Biogenic porous carbon silicon dioxide compositions and methods of making and using same

ABSTRACT

In various embodiments, the present disclosure provides biogenic porous carbon silicon dioxide compositions and methods of production and uses thereof.

PRIORITY CLAIM

This application is a 371 U.S. National Stage Application ofInternational patent Application No. PCT/US2019/036881 filed Jun. 13,2019, which claims priority to U.S. Provisional Patent Application Ser.No. 62/685,126, which was filed on Jun. 14, 2018, the entire contents ofwhich are incorporated herein by reference.

FIELD OF THE INVENTION

The present disclosure generally relates to biogenic porous carbonsilicon dioxide compositions and methods of making and uses thereof.

BACKGROUND

Use of biogenic porous carbon silicon dioxide compositions have thepotential to reduce the use, and environmental consequences of,non-renewable reagents in silicon production. Use of these biogenicporous carbon silicon dioxide compositions also have the potential toincrease throughput, decrease energy use, extend electrode life, creategreater purity silicon, allow use of small size silicon dioxide (quartz)in typical electric arc and submerged arc furnaces, and allow re-use ofsilica fume, thereby improving the production of silicon. Suchcompositions, and methods of making and using, are disclosed herein.

SUMMARY

The present disclosure provides for biogenic porous carbon silicondioxide compositions and methods of production and uses thereof.

Provided herein are high-carbon compositions comprising silicon dioxide.The compositions can comprise, on a dry basis: at least about 50 wt %total carbon, at most about 5 wt % hydrogen, at most about 1 wt %nitrogen, at most about 0.5 wt % phosphorus, at most about 0.2 wt %sulfur, at most about 0.02 wt % titanium, at most about 0.5% calcium, atmost about 0.1% aluminum, and silicon dioxide.

The compositions can comprise, on a dry basis: at least about 50 wt %total carbon, at most about 5 wt % hydrogen, at most about 1 wt %nitrogen, at most about 0.5 wt % phosphorus, at most about 0.2 wt %sulfur, at most about 0.02 wt % titanium, at most about 0.5% calcium, atmost about 0.1% aluminum, and silicon dioxide; wherein the silicondioxide can be comprised within river rock.

The compositions can comprise, on a dry basis: at least about 50 wt %total carbon, at most about 5 wt % hydrogen, at most about 1 wt %nitrogen, at most about 0.5 wt % phosphorus, at most about 0.2 wt %sulfur, at most about 0.02 wt % titanium, at most about 0.5% calcium, atmost about 0.1% aluminum, and silicon dioxide; wherein the silicondioxide can be comprised within silica fume.

In some embodiments, the carbon comprises biogenic carbon. In someembodiments, the carbon comprises non-biogenic carbon. The compositionscan comprise at least about 55 wt %, at least about 60 wt %, at leastabout 65 wt %, at least about 70 wt %, at least about 75 wt %, at leastabout 80 wt %, at least about 90 wt %, or at least about 95 wt % totalcarbon. In some embodiments, the composition comprises at least about 55wt % total carbon.

The compositions can comprise at least about 1 wt %, at least about 5 wt%, at least about 10 wt %, at least about 15 wt %, at least about 20 wt%, or at least about 25 wt % silicon dioxide.

In some embodiments, the silicon dioxide is comprised within river rock.In some embodiments, the silicon dioxide comprises silica fume.

In some embodiments, the compositions have been extruded. In someembodiments, the compositions have been extruded to form a pellet. Insome embodiments, the compositions have been extruded to improve thedensity of the composition; mix the carbon and silicon dioxide; improvethe combined product density, thereby allowing it to “sink” in anelectric arc furnace; or create a water and dust resistant exterior ofthe composition for improved use and improved furnace efficiencies.

In some embodiments, the compositions have been densified.

In some embodiments, the compositions have dimensions of at least about0.64 cm (0.25 in) by about 2.5 cm (1.0 in) to at most about 5.1 cm (2.0in) by about 15 cm (6.0 in).

In some embodiments, the compositions have a bulk density of about 560kg/m³ (35 lb/ft³) to about 720 kg/m³ (45 lb/ft³).

In some embodiments, the compositions have an Iodine Number of at leastabout 300.

In some embodiments, the compositions have a moisture (H₂O) content offrom about 1% to about 45%. In some embodiments, the compositions have amoisture (H₂O) content of less than about 1%.

The compositions can comprise a high-carbon reagent compositioncomprising, on a dry basis: at least about 50 wt % total carbon, at mostabout 5 wt % hydrogen, at most about 1 wt % nitrogen, at most about 0.5wt % phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andat least about 15 wt % silicon dioxide; wherein the silicon dioxide canbe comprised within river rock; and wherein the composition can bedensified, can be pellet shaped with dimensions of about 0.64 cm (0.25in) by about 2.5 cm (1.0 in), and can have a bulk density of about 560kg/m³ (35 lb/ft³) to about 720 kg/m³ (45 lb/ft³).

The compositions can comprise a high-carbon reagent compositioncomprising, on a dry basis: at least about 50 wt % total carbon, at mostabout 5 wt % hydrogen, at most about 1 wt % nitrogen, at most about 0.5wt % phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andat least about 15 wt % silicon dioxide; wherein the silicon dioxide canbe comprised within silica fume; and wherein the composition can bedensified, can be pellet shaped with dimensions of about 0.64 cm (0.25in) by about 2.5 cm (1.0 in), and can have a bulk density of about 560kg/m³ (35 lb/ft³) to about 720 kg/m³ (45 lb/ft³).

Provided herein are processes for producing a high-carbon biogenicreagent. The processes can comprise: providing a carbon-containingfeedstock comprising dry biomass; in a preheating zone, preheating thefeedstock in the presence of a substantially inert gas for at leastabout 5 minutes and with a preheating temperature selected from about80° C. to about 500° C.; in a pyrolysis zone, pyrolyzing the feedstockin the presence of a substantially inert gas for at least about 10minutes and with a pyrolysis temperature selected from about 250° C. toabout 700° C., to generate hot pyrolyzed solids, condensable vapors, andnon-condensable gases; separating at least a portion of the condensablevapors and at least a portion of the non-condensable gases from the hotpyrolyzed solids; in a cooling zone, cooling the hot pyrolyzed solids,in the presence of the substantially inert gas for at least about 5minutes and with a cooling temperature less than the pyrolysistemperature, to generate warm pyrolyzed solids; in a cooler that isseparate from the cooling zone, cooling the warm pyrolyzed solids togenerate cool pyrolyzed solids; and recovering a high-carbon biogenicreagent comprising at least a portion of the cool pyrolyzed solids;wherein the process further comprises introducing silicon dioxidefeedstock into the process.

In some embodiments, the processes further comprise drying the feedstockto remove at least a portion of moisture contained within the feedstock.

In some embodiments, the processes further comprise deaerating thefeedstock or the dried feedstock to remove at least a portion ofinterstitial oxygen, if any, contained with the feedstock.

In some embodiments, the processes further comprise, in a cooler that isseparate from the cooling zone, further cooling the warm pyrolyzedsolids to generate cool pyrolyzed solids.

In some embodiments, the processes further comprise introducing silicondioxide feedstock to the cool pyrolyzed solids. In some embodiments, theprocesses further comprise introducing silicon dioxide feedstock to thefeedstock prior to pyrolysis.

In some embodiments, introducing silicon dioxide feedstock comprisesintroducing silica fume. In some embodiments, introducing silicondioxide comprises introducing river rock. In some embodiments, theparticle size of the silicon dioxide feedstock, whether river rock orsilica fume, can be from about 0.01 mm to about 12 mm. In someembodiments, the particle size can be from about 0.01 mm to about 12 mm,in increments of about 0.05 mm.

In some embodiments, the processes further comprise densification.

In some embodiments, densification can comprise: using an additive forimproved densification; mixing of the additive, carbon, and silicondioxide; extruding the mixture through a die to thereby produce pellets;and optionally drying the pellets.

In some embodiments, densification can comprise: optionally using anadditive, for example, bentonite, for improved densification from about0.5% to about 15%, in increments of about 0.5%; optionally adding water,for example, from about 5% to about 50% water; mixing of the additive,carbon, and silicon dioxide; extruding the mixture through a die tothereby produce pellets; optionally heating or cooling the extruderand/or die plate to improve densification; optionally degassing theextruder; and optionally drying the pellets.

In some embodiments, the processes further comprise pressing, binding,pelletizing, extruding, or agglomerating the high-carbon biogenicreagent.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a multi-reactor embodiment of a system of the invention.

FIG. 2 depicts a single reactor, multi-zone embodiment of a system ofthe invention

FIG. 3 depicts one embodiment of a zero-oxygen continuous feed mechanismsuitable for use in connection with the present invention.

FIG. 4 depicts another embodiment of a single reactor, multi-zonebiomass processing unit suitable for use in connection with the presentinvention.

FIG. 5 depicts one embodiment of a carbon recovery unit suitable for usein connection with the present invention.

FIG. 6 depicts an embodiment of one embodiment of a single-reactorbiomass processing unit of the present invention with an optional dryer.

FIG. 7 depicts a pyrolysis reactor system embodiment of the inventionwith an optional dryer and a gas inlet.

FIG. 8 depicts an embodiment of a single-reactor biomass processing unitof the invention with a gas inlet and an optional cooler.

FIG. 9 depicts a single-reactor biomass processing unit systemembodiment of the invention with an optional dryer and de-aerator, andan inert gas inlet.

FIG. 10 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer and de-aerator, and an inert gas inlet.

FIG. 11 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer and cooler, and a material enrichment unit.

FIG. 12 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer, de-aerator, a cooler, and an inert gas inlet.

FIG. 13 depicts a multiple-reactor system embodiment of the inventionwith an optional dryer and de-aerator, an inert gas inlet, and a cooler.

FIG. 14 depicts a single-reactor biomass processing unit embodiment ofthe disclosure for producing biogenic activated carbon.

FIG. 15 depicts a two-reactor biomass processing unit embodiment of thedisclosure for producing biogenic activated carbon.

DETAILED DESCRIPTION

The present disclosure provides for biogenic porous carbon silicondioxide compositions and methods of production and uses thereof.

This description will enable one skilled in the art to make and use thedisclosure, and it describes several embodiments, adaptations,variations, alternatives, and uses of the disclosure. These and otherembodiments, features, and advantages of the present disclosure willbecome more apparent to those skilled in the art when taken withreference to the following detailed description of the disclosure inconjunction with the accompanying drawings.

Definitions

As used herein, the term “at most” provides for a minimum value of“trace amounts.”

As used herein, the term “carbon” can mean biogenic or non-biogeniccarbon. “Biogenic” is intended to mean a material (whether a feedstock,product, or intermediate) that contains an element, such as carbon, thatis renewable on time scales of months, years, or decades. Non-biogenicmaterials can be non-renewable, or can be renewable on time scales ofcenturies, thousands of years, millions of years, or even longergeologic time scales. A biogenic material may include a mixture ofbiogenic and non-biogenic sources.

As used herein, the term “biomass,” shall be construed as any biogenicfeedstock or mixture of a biogenic and non-biogenic feedstock.Elementally, biomass includes at least carbon, hydrogen, and oxygen. Themethods and apparatus of the disclosure can accommodate a wide range offeedstocks of various types, sizes, and moisture contents.

As used herein, the term “activation” refers to any of the variousprocesses by which the pore structure is enhanced.

As used herein, the phrase “porous carbon” describes materials that canbe produced by processes and systems of the disclosure, in variousembodiments. Limitations as to carbon content, or any otherconcentrations, shall not be imputed from the term itself but ratheronly by reference to particular embodiments and equivalents thereof. Forexample, it will be appreciated that a starting material having very lowinitial carbon content, subjected to the disclosed processes, mayproduce a biogenic porous carbon that is highly enriched in carbonrelative to the starting material (high yield of carbon), butnevertheless relatively low in carbon (low purity of carbon), includingless than or equal to about 50 wt % carbon.

As used herein, the term “silicon dioxide” (SiO₂) is interchangeablewith the term “silica.”

As used herein, the term “reagent” is intended to mean a material in itsbroadest sense; a reagent can be, for example, a fuel, a chemical, amaterial, a compound, an additive, a blend component, a solvent. Areagent is not necessarily a chemical reagent that causes orparticipates in a chemical reaction. A reagent may or may not be achemical reactant; it may or may not be consumed in a reaction. Areagent can be a chemical catalyst for a particular reaction. A reagentmay cause or participate in adjusting a mechanical, physical, orhydrodynamic property of a material to which the reagent can be added.For example, a reagent can be introduced to a metal to impart certainstrength properties to the metal. A reagent can be a substance ofsufficient purity (which, in the current context, is typically carbonpurity) for use in chemical analysis or physical testing.

As used herein, the terms “pyrolysis” and “pyrolyze” generally refer tothermal decomposition of a carbonaceous material.

As used herein, the term “reactor” refers to a discrete unit in whichatmospheric and temperature conditions can be controlled and in which aphysical and/or chemical reaction can take place.

As used herein, the term “zone” refers to an area within a reactor inwhich temperature conditions and atmospheric conditions can becontrolled relative to other zones within the reactor.

As used herein, the term “biomass processing unit” refers to a reactorthat includes a plurality of zones as discussed in more detail below.

As used herein, the term “carbonization” herein means increasing thecarbon content in a given amount of biomass. Carbonization canillustratively be accomplished by reducing non-carbon containingmaterial from the biomass, adding carbon atoms to the biomass or both toform a “high-carbon biogenic reagent.”

As used herein, where the indefinite article “a” or “an” is used withrespect to a statement or description of the presence of a step in aprocess disclosed herein, unless the statement or description explicitlyprovides to the contrary, the use of such indefinite article does notlimit the presence of the step in the process to one in number. As usedherein, when an amount, concentration, or other value or parameter isgiven as either a range, preferred range, or a list of upper preferablevalues and lower preferable values, this is to be understood asspecifically disclosing all ranges formed from any pair of any upperrange limit or preferred value and any lower range limit or preferredvalue, regardless of whether ranges are separately disclosed.

Where a range of numerical values is recited herein, unless otherwisestated, the range is intended to include the endpoints thereof, and allintegers and fractions within the range. It is not intended that thescope of the invention be limited to the specific values recited whendefining a range.

As used herein, the terms “comprising” and “including”, or grammaticalvariants thereof are to be taken as specifying inclusion of the statedfeatures, integers, actions or components without precluding theaddition of one or more additional features, integers, actions,components or groups thereof. For example, a composition, a mixture,process, method, article, or apparatus that comprises a list of elementsis not necessarily limited to only those elements but can include otherelements not expressly listed or inherent to such composition, mixture,process, method, article, or apparatus. “Comprising” is broader than andincludes the terms “consisting of” and “consisting essentially of” asdefined by the Manual of Patent Examination Procedure of the UnitedStates Patent and Trademark Office. Further, unless expressly stated tothe contrary, “or” refers to an inclusive or and not to an exclusive or.

Unless otherwise indicated, all numbers expressing reaction conditions,stoichiometries, concentrations of components, and so forth used in thespecification and claims are to be understood as being modified in allinstances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the followingspecification and attached claims are approximations that may varydepending at least upon a specific analytical technique.

Compositions

Provided herein are biogenic carbon compositions comprising silicondioxide. The compositions can comprise, on a dry basis: at least about50 wt % total carbon, at most about 5 wt % hydrogen, at most about 1 wt% nitrogen, at most about 0.5 wt % phosphorus, at most about 0.2 wt %sulfur, at most about 0.02 wt % titanium, at most about 0.5% calcium, atmost about 0.1% aluminum, and silicon dioxide.

The compositions can comprise, on a dry basis: at least about 55 wt %,at least about 60 wt %, at least about 65 wt %, at least about 70 wt %,at least about 75 wt %, at least about 80 wt %, at least about 90 wt %,or at least about 95 wt % total carbon; at most about 5 wt % hydrogen;at most about 1 wt % nitrogen; at most about 0.5 wt % phosphorus; atmost about 0.2 wt % sulfur; at most about 0.02 wt % titanium; at mostabout 0.5% calcium; at most about 0.1% aluminum; and at least about 1 wt%, at least about 5 wt %, at least about 10 wt %, at least about 15 wt%, at least about 20 wt %, or at least about 25 wt % silicon dioxide.

The compositions can comprise, on a dry basis: at least about 50 wt %total carbon, at most about 5 wt % hydrogen, at most about 1 wt %nitrogen, at most about 0.5 wt % phosphorus, at most about 0.2 wt %sulfur, at most about 0.02 wt % titanium, at most about 0.5% calcium, atmost about 0.1% aluminum, and at least about 15 wt % silicon dioxide;wherein the silicon dioxide is comprised within river rock; and whereinthe composition has been densified, is pellet shaped with dimensions ofat least about 0.64 cm (0.25 in) by about 2.5 cm (1.0 in), and has abulk density of about 560 kg/m³ (35 lb/ft³) to about 720 kg/m³ (45lb/ft³).

The compositions can comprise, on a dry basis: at least about 50 wt %total carbon, at most about 5 wt % hydrogen, at most about 1 wt %nitrogen, at most about 0.5 wt % phosphorus, at most about 0.2 wt %sulfur, at most about 0.02 wt % titanium, at most about 0.5% calcium, atmost about 0.1% aluminum, and at least about 15 wt % silicon dioxide;wherein the silicon dioxide is comprised within silica fume; and whereinthe composition has been densified, is pellet shaped with dimensions ofat least about 0.64 cm (0.25 in) by at least about 2.5 cm (1.0 in), andhas a bulk density of about 560 kg/m³ (35 lb/ft³) to about 720 kg/m³ (45lb/ft³).

The compositions can comprise at least about 55 wt %, at least about 60wt %, at least about 65 wt %, at least about 70 wt %, at least about 75wt %, at least about 80 wt %, at least about 90 wt %, or at least about95 wt % total carbon.

The compositions can comprise at least about 1 wt %, at least 5 wt %, atleast about 10 wt %, at least about 15 wt %, at least about 20 wt %, orat least about 25 wt % silicon dioxide.

In some embodiments, the starting material for producing biogenic carboncompositions has a very low initial carbon content however, oncesubjected to the disclosed processes, the resulting composition ishighly enriched in carbon relative to the starting material (high yieldof carbon), but nevertheless relatively low in carbon (low purity ofcarbon), including less than or equal to about 50 wt % carbon. Thebiogenic carbon of the present disclosure has relatively high carboncontent compared to the initial feedstock utilized to produce thebiogenic carbon. The biogenic carbon will normally contain greater thanabout half its weight as carbon, since the typical carbon content ofbiomass is no greater than about 50 wt %. More typically, but dependingon feedstock composition, a biogenic carbon will contain at least about55 wt %, at least about 60 wt %, at least about 65 wt %, at least about70 wt %, at least about 75 wt %, at least about 80 wt %, at least about85 wt %, at least about 90 wt %, at least about 95 wt %, at least about96 wt %, at least about 97 wt %, at least about 98 wt %, or at leastabout 99 wt % carbon.

In some embodiments, the biogenic carbon composition has been activated.Activation refers to any process by which the resulting pore size of thecarbon is enhanced. Conventional processes for producing porous carbonrequire large energy inputs and suffer from low yields.

Various embodiments of the present disclosure use carbon-containingfeedstocks other than biomass, such as a fossil fuel (e.g., coal orpetroleum coke), or any mixtures of biomass and fossil fuels (such asbiomass/coal blends). In some embodiments, a biogenic feedstock is, orincludes, coal, oil shale, crude oil, asphalt, or solids from crude-oilprocessing (such as petcoke). Feedstocks may include waste tires,recycled plastics, recycled paper, and other waste or recycledmaterials. Any method, apparatus, or system described herein can be usedwith any carbonaceous feedstock. Carbon-containing feedstocks can betransportable by any known means, such as by truck, train, ship, barge,tractor trailer, or any other vehicle or means of conveyance.

In some embodiments, the biogenic carbon composition of the presentdisclosure comprises silicon dioxide (SiO₂). In some embodiments, theSiO₂ can be raw SiO₂. In another embodiment, the SiO₂ is comprisedwithin river rock or quartz. In yet another embodiment, the SiO₂ can becomprised within silica fume.

In some embodiments, the composition is a reagent. In some embodiments,the composition is a biogenic carbon reagent. In another embodiment, thecomposition is high-carbon biogenic reagent.

In some embodiments, the composition has been extruded. Extrusion can beutilized to, for example, modify particle sizes of the carbon in orderto enhance density; mix the carbon and silicon dioxide; enhance combinedproduct density, so as to produce a product that will “sink” in anelectric arc furnace; and create a water and dust resistant exterior ofthe extrudate for improved use and improved furnace efficiencies.

In some embodiments, the composition has been densified. A process ofdensification is described in more detail below.

In some embodiments, the compositions are pellet shaped. In someembodiments, the compositions can have dimensions of at least about 0.64cm (0.25 in) by about 2.5 cm (1.0 in) to at most about 5.1 cm (2.0 in)by about 15 cm (6.0 in). For example, the composition can have theparticle sizes as shown in Table 1 below.

TABLE 1 Particle size of the silicon dioxide porous carbon according tothe present disclosure. Sample Weight Total: 56 Weight Retained %Retained  4 mesh 2.2 0.039 3.9  8 mesh 5.7 0.102 10.2 20 mesh 23.4 0.41841.8 30 mesh 12.7 0.227 22.7 100 mesh  10.8 0.193 19.3 −100 mesh    0.10.002 0.2

In some embodiments, the composition can have a bulk density of about560 kg/m³ (35 lb/ft³) to about 720 kg/m³ (45 lb/ft³). In someembodiments, the bulk density of the compositions can be about 550 kg/m³(34 lb/ft³), about 560 kg/m³ (35 lb/ft³), about 570 kg/m³ (36 lb/ft³),about 580 kg/m³ (36 lb/ft³), about 590 kg/m³ (37 lb/ft³), about 600kg/m³ (37 lb/ft³), about 610 kg/m³ (38 lb/ft³), about 620 kg/m³ (39lb/ft³), about 630 kg/m³ (39 lb/ft³), about 640 kg/m³ (40 lb/ft³), about650 kg/m³ (41 lb/ft³), about 660 kg/m³ (41 lb/ft³), about 670 kg/m³ (42lb/ft³), about 680 kg/m³ (42 lb/ft³), about 690 kg/m³ (43 lb/ft³), about700 kg/m³ (44 lb/ft³), about 710 kg/m³ (44 lb/ft³), about 720 kg/m³ (45lb/ft³), about 730 kg/m³ (46 lb/ft³), about 740 kg/m³ (46 lb/ft³), orabout 750 kg/m³ (47 lb/ft³). In some embodiments, the bulky density ofthe compositions is about 560 kg/m³ (35 lb/ft³) to about 720 kg/m³ (45lb/ft³), about 650 kg/m³ (41 lb/ft³) to about 700 kg/m³ (44 lb/ft³),about 670 kg/m³ (42 lb/ft³) to about 710 kg/m³ (44 lb/ft³), or about 630kg/m³ (39 lb/ft³) to about 730 kg/m³ (46 lb/ft³).

Increased porosity improves reactivity of the carbon and facilitatesconversion of the compositions to pure silicon. The compositions can beiodine number of at least about 300. The Iodine Number is a parameterused to characterize porous carbon performance. The Iodine Numbermeasures the degree of activation of the carbon, and is a measure ofmicropore (e.g., 0-20 Å) content. It is an important measurement forliquid-phase applications. In some embodiments, the porous carbonproducts produced by embodiments of the disclosure have an Iodine Numberof about 300, about 400, about 500, about 600, about 750, about 900,about 1000, about 1100, about 1200, about 1300, about 1500, about 1600,about 1750, about 1900, about 2000, about 2100, and about 2200. In someembodiments, the porous carbon products produced by the embodiments ofthe disclosure have an Iodine Number of at least about 300, at leastabout 400, at least about 500, at least about 600, at least about 750,at least about 900, at least about 1000, at least about 1100, at leastabout 1200, at least about 1300, at least about 1500, at least about1600, at least about 1750, at least about 1900, at least about 2000, atleast about 2100, and at least about 2200. In yet another embodiment,the porous carbon products produced by the embodiments of the disclosurehave an Iodine Number of about 300 to about 2200, about 500 to about1500, about 750 to about 1750, about 900 to about 1300, about 1000 toabout 1500, about 1500 to about 2200, or about 1200 to about 1900.

Processes

Provided herein are processes for producing a high-carbon biogenicreagent. In some embodiments, the processes can comprise: providing acarbon-containing feedstock comprising dry biomass; in a preheatingzone, preheating the feedstock in the presence of a substantially inertgas for at least about 5 minutes and with a preheating temperatureselected from about 80° C. to about 500° C.; in a pyrolysis zone,pyrolyzing the feedstock in the presence of a substantially inert gasfor at least about 10 minutes and with a pyrolysis temperature selectedfrom about 250° C. to about 700° C., to generate hot pyrolyzed solids,condensable vapors, and non-condensable gases; separating at least aportion of the condensable vapors and at least a portion of thenon-condensable gases from the hot pyrolyzed solids; in a cooling zone,cooling the hot pyrolyzed solids, in the presence of the substantiallyinert gas for at least about 5 minutes and with a cooling temperatureless than the pyrolysis temperature, to generate warm pyrolyzed solids;in a cooler that is separate from the cooling zone, cooling the warmpyrolyzed solids to generate cool pyrolyzed solids; and recovering ahigh-carbon biogenic reagent comprising at least a portion of the coolpyrolyzed solids; wherein the process further comprises introducingsilicon dioxide into the process.

There is disclosed herein a process for producing a high-carbon biogenicreagent, the process comprising: providing a carbon-containing feedstockcomprising biomass; optionally drying the feedstock to remove at least aportion of moisture contained within the feedstock; optionallydeaerating the feedstock or the dried feedstock to remove at least aportion of interstitial oxygen, if any, contained with the feedstock; ina pyrolysis zone, pyrolyzing the feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non condensablegases; separating at least a portion of the condensable vapors and atleast a portion of the non-condensable gases from the hot pyrolyzedsolids; in a cooling zone, cooling the hot pyrolyzed solids, in thepresence of the substantially inert gas for at least about 5 minutes andwith a cooling-zone temperature less than the pyrolysis temperature, togenerate warm pyrolyzed solids; in an optional cooler that is separatefrom the cooling zone, further cooling the warm pyrolyzed solids togenerate cool pyrolyzed solids; and recovering a high-carbon biogenicreagent comprising at least a portion of the warm or cool pyrolyzedsolids.

In some embodiments, during pyrolysis, less oxygen is present in anamount less than is required to complete combustion of the material. Insome embodiments, the oxygen is present in less than or equal to about10%, less than or equal to about 5%, less than or equal to about 1%,less than or equal to about 0.5%, less than or equal to about 0.1%, orless than or equal to about 0.01% of the oxygen that is required forcomplete combustion. In some embodiments, pyrolysis is performed in theabsence of oxygen.

In some embodiments, the processes for producing a high-carbon biogenicreagent include a reactor. In some embodiments, the reactor is adiscrete unit in which atmospheric temperature and conditions can becontrolled. In some embodiments, the reaction takes place in thereactor. In another embodiment, the reactor can include one or morezones. In some embodiments, the one or more zones is an area within thereactor in which the temperature and atmospheric conditions can becontrolled relative to other zones within the reactor.

In various embodiments, the processes for producing a high-carbonbiogenic reagent include a biomass processing unit (“BPU”). In someembodiments, the BPU includes a plurality of output passagewaysconfigured to transfer the raw material or feedstock at different stagesof processing, gases, condensate byproducts, and heat from variousreactors and zones to any one or more of the other reactors or zones,the material feed system, the carbon recovery unit, and any othercontemplated components of the system described herein. In oneembodiment, after the raw material has passed through each of the zonesof the BPU, the raw material is carbonized.

In some embodiments, the processes for producing a high-carbon biogenicreagent include carbonization. In some embodiments, carbonization canillustratively be accomplished by reducing non-carbon containingmaterial from the biomass, adding carbon atoms to the biomass or both toform a “high-carbon biogenic reagent.”

As discussed below, various multi-zone BPU embodiments include a singlereactor and various multi-zone BPU embodiments could also include morethan one separate reactor. It should be appreciated that otherembodiments discussed below include multiple separate reactors, eachreactor having at least one zone. For the purposes of this disclosure,the properties, principles, processes, alternatives, and embodimentsdiscussed with respect to all single reactor multi-zone BPU embodimentsapply equally to all multiple separate reactor embodiments, andvice-versa.

In some embodiments, the process comprises drying the feedstock toremove at least a portion of moisture contained within the feedstock. Inthese or other embodiments, the process comprises deaerating thefeedstock to remove at least a portion of interstitial oxygen containedwith the feedstock.

The process may further include preheating the feedstock, prior to step(d), in a preheating zone in the presence of the substantially inert gasfor at least about 5 minutes and with a preheating temperature selectedfrom about 80° C. to about 500° C., or from about 300° C. to about 400°C.

In some embodiments, the pyrolysis temperature is selected from about400° C. to about 600° C. In some embodiments, pyrolysis in step (d) iscarried out for at least about 20 minutes. The cooling-zone temperaturemay be selected from about 150° C. to about 350° C., for example.

Pyrolysis conditions may be selected to maintain the structuralintegrity or mechanical strength of the high-carbon biogenic reagentrelative to the feedstock, when it is desired to do so for a certainproduct application.

In some embodiments, each of the zones is located within a singlereactor or a BPU. In other embodiments, each of the zones is located inseparate BPUs or reactors. It should be appreciated that someembodiments include one or more BPUs, each including at least one zone.

The substantially inert gas may be selected from the group consisting ofN₂, Ar, CO, CO₂, H₂, CH₄, and combinations thereof. Some of thesubstantially inert gas may include one or more non-condensable gasspecies (e.g., CO and CO₂) recycled from step (e). In some embodiments,the pyrolysis zone and the cooling zone each comprise a gas phasecontaining less than 5 wt % oxygen, such as about 1 wt % oxygen or less.

The process may be continuous, semi-continuous, or batch. In somecontinuous or semi-continuous embodiments, the inert gas flowssubstantially countercurrent relative to the direction of solids flow.In other continuous or semi-continuous embodiments, the inert gas flowssubstantially concurrent relative to the direction of solids flow.

In some embodiments, the process includes monitoring and controlling theprocess with at least one reaction gas probe, such as two or morereaction gas probes. Monitoring and controlling the process can improveprocess energy efficiency. Monitoring and controlling the process canalso improve a product attribute associated with the high-carbonbiogenic reagent, such as (but not limited to) carbon content, energycontent, structural integrity, or mechanical strength.

The process may further include thermal oxidation (i.e., combustion) ofat least a portion of the condensable and non-condensable vapors with anoxygen-containing gas. The thermal oxidation may be assisted withcombustion of natural gas. Heat produced from the thermal oxidation maybe utilized, at least in part, for drying the feedstock. Additionally,heat produced from the thermal oxidation may be utilized, at least inpart, to heat the substantially inert gas before entering one of thezones or reactors, such as the pyrolysis zone.

The process may further include combining at least a portion of thevapors with the cooled pyrolyzed solids, to increase the carbon contentof the high-carbon biogenic reagent. Alternatively, or additionally, theprocess may further include combining at least a portion of thecondensable vapors with the warm pyrolyzed solids, to increase thecarbon content of the high-carbon biogenic reagent.

Condensable vapors may thus be used for either energy in the process(such as by thermal oxidation) or in carbon enrichment, to increase thecarbon content of high-carbon biogenic reagent. Certain non-condensablegases, such as CO or CH₄, may be utilized either for energy in theprocess, or as part of the substantially inert gas for the pyrolysisstep.

In some embodiments, the process further comprises introducing at leastone additive selected from acids, bases, or salts thereof. The additivemay be selected from (but not limited to) the group consisting of sodiumhydroxide, potassium hydroxide, magnesium oxide, hydrogen bromide,hydrogen chloride, sodium silicate, potassium permanganate, andcombinations thereof.

In some embodiments, the process further comprises introducing at leastone additive selected from the group consisting of a metal, a metaloxide, a metal hydroxide, a metal halide, and combinations thereof. Theadditive may be selected from (but not limited to) the group consistingof magnesium, manganese, aluminum, nickel, chromium, silicon, boron,cerium, molybdenum, phosphorus, tungsten, vanadium, iron halide, ironchloride, iron bromide, magnesium oxide, dolomite, dolomitic lime,fluorite, fluorspar, bentonite, calcium oxide, lime, and combinationsthereof.

Additives, including silicon dioxide or silica fume, may be addedbefore, during, or after any one or more steps of the process, includinginto the feedstock itself at any time, before or after it is harvested.Additives may be introduced prior to or during step (b), prior to orduring step (d), during step (f), during step (g), between steps (f) and(g), or after step (g), for example. An additive may be introduced tothe warm pyrolyzed solids. For example, an additive may be introduced inan aqueous solution, vapor, or aerosol to assist with cooling of thewarm pyrolyzed solids in step (g). In these or other embodiments, anadditive is introduced to the cool pyrolyzed solids to form thehigh-carbon biogenic reagent containing the additive.

In some embodiments, the process further comprises introducing at leasta portion of the cool pyrolyzed solids to a separate unit for additionalpyrolysis, in the presence of a substantially inert gas for at leastabout 30 minutes and with a pyrolysis temperature selected from about200° C. to about 600° C., to generate a solid product having highercarbon content than the cool pyrolyzed solids.

In some embodiments, the process further comprises operating a cooler tocool the warm pyrolyzed solids with steam, thereby generating the coolpyrolyzed solids and superheated steam; wherein the drying is carriedout, at least in part, with the superheated steam derived from theexternal cooler. Optionally, the cooler may be operated to first coolthe warm pyrolyzed solids with steam to reach a first coolertemperature, and then with air to reach a second cooler temperature,wherein the second cooler temperature is lower than the first coolertemperature and is associated with a reduced combustion risk for thewarm pyrolyzed solids in the presence of the air.

In the processes disclosed herein, introducing silicon dioxide cancomprise introducing silica fume. Silica fume is an ultrafine(comprising particles generally less than 1 μm in diameter) silicapowder byproduct from silicon production, for example, in the productionof silicon metal or ferrosilicon alloys, during which it is captured inbaghouses. Silicon metal and alloys are produced in electric furnaces.Silica fume consists primarily of amorphous (non-crystalline) silicondioxide.

In the processes disclosed herein, introducing silicon dioxide cancomprise introducing raw silicon dioxide. For example, introducingsilicon dioxide can comprise introducing river rock or quartz. Freesilica occurs in many crystalline forms with a composition very close tothat of silicon dioxide, e.g., 46.75% by weight being silicon and 53.25%oxygen. Quartz is by far the most commonly occurring form. Tridymite,cristobalite, and the hydrous silica mineral opal are uncommon, andvitreous (glassy) silica, coesite, and stishovite have been reportedfrom only a few localities.

Silicon dioxide, whether introduced as silica fume or river rock, can beintroduced into the process by adding silicon dioxide to cooledpyrolyzed solids after pyrolysis. Silicon dioxide, whether introduced assilica fume or river rock, can be introduced prior to pyrolysis, and thesilicon dioxide can improve heat transfer thereby leading to theimproved pyrolysis of biomass.

The silicon dioxide, as comprised within a raw material feedstock suchas silica fume or river rock, that is introduced can be smaller thanwhat has heretofore been used in a submerged arc or electric arcfurnace. For example, the particle size of the silicon dioxidefeedstock, whether river rock or silica fume, can be from about 0.01 mmto about 12 mm. For example, the particle size can be from about 0.01 mmto 12 mm, in increments of about 0.05 mm.

The process can further comprise pressing, binding, pelletizing,extruding, or agglomerating the composition.

The processes can further comprise densification, thereby producing, forexample, a pellet shaped composition. Other shapes can be produced. Forexample, spheres. The proximity of the carbon and silicon dioxide in thedensified composition results in more efficient conversion of thecomposition to silicon.

A densification process can create a final composition of materials.Densification allows materials to be mixed and blended in a controlledmanner with other particles comprising a composition as describedherein. A composition as described can be processed and forced throughdensification equipment. Such equipment can include commerciallyavailable machines. Densification equipment forces a composition througha shaping die, thereby producing, for example, a pellet. Faceplatetemperature of the extrusion equipment typically is between about 72° C.(165° F.) and about 85° C. (185° F.). A pellet can exit at a temperatureof about 43° C. (110° F.) and not greater than about 121° C. (250° F.).When a pellet exits the extruder, there can be a slight coating on theexternal surface of the pellet. This coating can comprise lignin, whichis a naturally occurring substance of the cellulosic material. Pelletscan then be transferred to the finished object conveyor/cooler.

Following formation, pellets can be cooled down by a cooling meansincluding, but not limited to, an air cooler, an air conditioner, orliquid nitrogen. The cooling process causes the pellets to harden intothe shape created by the extruder and allows components of the pellet tomaintain their integrity. In one embodiment, pellets are placed througha shaker screen after sufficiently cooling and hardening. This separatesfine and discrete particles. The discharge for the fine particles can beseparated and can again be recycled or forced through an extruder. Thiscan minimize the potential for waste generated by any excess particlesthat comprise a pellet.

A densification process can comprise: using an additive for improveddensification; mixing of the additive, carbon, and silicon dioxide;extruding the mixture through a die to thereby produce pellets; andoptionally drying the pellets.

A densification process can comprise: optionally using an additive, forexample, bentonite, for improved densification from about 0.5% to about15%, in increments of about 0.5%; optionally adding water, for example,from about 5% to about 50% water; mixing of the additive, carbon, andsilicon dioxide; extruding the mixture through a die to thereby producepellets; optionally heating or cooling the extruder and/or die plate toimprove densification; optionally degassing the extruder; and optionallydrying the pellets.

Extruders can also be used to shape and mix materials. Extrusion is aprocess used to create objects of a fixed cross-sectional profile. Amaterial is pushed through a die of the desired cross-section. The twomain advantages of this process over other manufacturing processes areits ability to create very complex cross-sections, and to work materialsthat are brittle, because the material only encounters compressive andshear stresses. It also forms products with an excellent surface finish.Extrusion may be continuous (theoretically producing indefinitely longmaterial) or semi-continuous (producing many pieces). The extrusionprocess can be done with the material hot or cold. Various binders,coatings, and extrusion recipes can be used to achieve varying productattributes ranging from >99% on the “pellet durability index” to dustfree to hydrophobicity. Die thickness, die taper, screw speed, moisturecontent, pre-compaction, product sizing, and numerous other variablescan impact pellet quality. For example, if more moisture is used duringextrusion, and the product is then dried, it is easier to apply awax-based coating than if less water is used in extrusion.

Referring generally to FIGS. 1 to 13, block flow diagrams of a severalexemplary multi reactor embodiments of the present disclosure areillustrated. Each figure is discussed in turn below. It should beappreciated FIGS. 1 to 13 represent some example embodiments but not allcontemplated embodiments of the present disclosure. As discussed below,various additional non-illustrated embodiments and combinations of theseveral components and features discussed herein are also contemplated.As will be understood in the discussion below, any of the plurality ofreactors discussed herein can be independent reactors, or alternativelywithin a single reactor BPU can include a plurality of zones, or acombination thereof. It should be appreciated that, although the figureseach illustrate a different alternative embodiment, all other discussionin this disclosure can apply to each of the illustrated andnon-illustrated embodiments.

Referring now generally to FIG. 1, a block flow diagram of a multireactor embodiment of the present disclosure is illustrated. Thisembodiment can utilize two to a plurality of different reactors. Threereactors are shown in the illustrative embodiment; however, anydifferent number of reactors could be employed. In one embodiment, eachreactor is connected to at least one other reactor via a materialtransport unit 304 (shown in FIG. 3). In one embodiment, the materialtransport unit 304 controls atmosphere and temperature conditions.

In the illustrated embodiment, the raw material 109, such as biomass, isoptionally dried and sized outside the system and introduced into thefirst reactor 100 in a low-oxygen atmosphere, optionally through the useof a material feed system 108. As discussed in further detail below andas illustrated in FIG. 3, the material feed system 108 reduces theoxygen level in the ambient air in the system to not more than about 3%.The raw material 109 enters the first reactor 112 via the enclosedmaterial transport unit 304 after the oxygen levels have been decreasedin the first reactor. In one embodiment, the raw material transport unitwill include an encapsulated jacket or sleeve through which steam andoff-gases from the reactor are sent and used to pre-heat the biomasseither directly or sent to a process gas heater and or heat exchangerand then sent and used to pre-heat or pyrolyze the biomass.

In the illustrated embodiment, the raw material 109 first travels fromthe material feed system 108 on the material transport unit 304 into thefirst reactor of the BPU 112.

As discussed in more detail below, in one embodiment, the first reactor112 is configured to be connected to any other reactor in the system torecover waste heat 132 and conserve energy through a suitable waste heatrecovery system. In one embodiment, the waste heat given off in thefirst reactor 112 is used to operate a steaming bin or anotherappropriate heating mechanism configured to dry raw materials 109 insideor outside of the system. In various embodiments, other byproducts ofthe waste heat, such as a substantially heated inert gas or the like,can be used elsewhere in the system to further enrich the material atany point along the process.

In the illustrated embodiment, the biomass 109 enters the first reactor112, wherein the temperature is raised from the range of about ambienttemperature to about 150° C. to a temperature of about 100° C. to about200° C. In one embodiment, the temperature does not exceed 200° C. inthe first reactor 112. As discussed in greater detail below, the firstreactor 112 can include an output mechanism to capture and exhaustoff-gases 120 from the biomass 123 while it is being heated. In oneembodiment, the off-gases 120 are extracted for optional later use. Invarious embodiments, the heating source used for the various zones inthe BPU 102 is electrical or gas. In one embodiment, the heating sourceused for the various reactors of the BPU 102 is waste gas from otherreactors of the unit 102 or from external sources. In variousembodiments, the heat is indirect.

Following preheating in the first reactor 112, the material transportunit 304 passes the preheated material 123 into the optional secondreactor 114. In one embodiment reactor 114 is the same as reactor 112.In one embodiment where reactor 114 is different than reactor 112, thematerial transport unit 304 penetrates the second reactor 114 through ahigh-temperature vapor seal system (e.g. an airlock), which allows thematerial transport unit 304 to penetrate the second reactor whilepreventing gas from escaping. In one embodiment, the interior of thesecond reactor 114 is heated to a temperature of about 100° C. to about600° C. or about 200° C. to about 600° C. In another embodiment, thesecond reactor 114 includes an output port similar to the first reactor102 to capture and exhaust the gases 122 given off of the preheatedmaterial 123 while it is being carbonized. In one embodiment, the gases122 are extracted for optional later use. In one illustrativeembodiment, the off-gases 120 from the first reactor 112 and theoff-gases 122 from the second reactor 114 are combined into one gasstream 124. Once carbonized, the carbonized biomass 125 exits the secondreactor 114 and enters the third reactor 116 for cooling. Again, thethird reactor can be the same reactor as 112 or 114 or different.

In one embodiment, when the biogenic reagent 125 enters the thirdreactor 116, the carbonized biomass 125 is allowed to cool (actively orpassively) to a specified temperature range to form carbonized biomass126, as discussed above. In one embodiment, temperature of thecarbonized biomass 125 is reduced in the third reactor undersubstantially inert atmospheric conditions. In another embodiment, thethird reactor cools the carbonized biomass 125 with an additionalwater-cooling mechanism. It should be appreciated that the carbonizedbiomass 126 is allowed to cool in the third reactor 116 to the pointwhere it will not spontaneously combust if exposed to oxygenated air. Inone such embodiment, the third reactor 116 reduces temperature of thecarbonized biomass to below 200° C. In one embodiment, the third reactorincludes a mixer (not shown) to agitate and uniformly cool thecarbonized biomass. It should be appreciated that cooling may occureither directly or indirectly with water or other liquids; cooling mayalso occur either directly or indirectly with air or other cooled gases,or any combination of the above.

It should be appreciated that in several embodiments (not shown) one ormore additional coolers or cooling mechanisms are employed to furtherreduce the temperature of the carbonized biomass. In various suchembodiments, the cooler is separate from the other reactors 112, 114,116, along the material transport system. In some embodiments, thecooler follows the reactors. In some embodiments, the cooler can be thesame as the reactors 112, 114, 116. In other embodiments, the cooler is,for example, a screw, auger, conveyor (specifically a belt conveyor inone embodiment), drum, screen, pan, counterflow bed, vertical tower,jacketed paddle, cooled screw or combination thereof that cools eitherdirectly or indirectly with water or other liquids, or directly orindirectly with other gases, or combination of the above. In variousembodiments, coolers could include water spray, cooled inert gasstreams, liquid nitrogen, or ambient air if below ignition temperature.It should be appreciated that heat can be recovered from this step bycapturing the flash steam generated by the water spray, or thesuperheated steam generated when saturated steam is introduced andheated by the carbonized biomass.

As illustrated in FIGS. 1 and 5, the gas-phase separator unit 200includes at least one input and a plurality of outputs. The at least oneinput is connected to the exhaust ports on the first reactor 112 and thesecond reactor 114 of the BPU 102. One of the outputs is connected tothe carbon recovery unit 104, and another one of the outputs isconnected to collection equipment or further processing equipment suchas an acid hydrogenation unit 106 or distillation column. In variousembodiments, the gas-phase separator processes the off-gases 120, 122from the first reactor 112 and the second reactor 114 to produce acondensate 128 and an enrichment gas 204. In various embodiments,condensables may be used for either energy recovery (134) (for examplein the dryer, reactor or process gas heater), or for other carbonenrichment. In various embodiments, non-condensables (for example CO)may be used for energy recovery (134) (for example in a dryer, reactoror process gas heater), as an inert gas in the process (for example inthe deaeration unit, reactor, BPU or cooler discussed in more detailbelow) or for carbon enrichment.

In various embodiments, the condensate 128 includes polar compounds,such as acetic acid, methanol and furfural. In another embodiment, theenrichment gas 204 produced by the gas-phase separator 200 includes atleast non-polar gases, for example carbon monoxide, terpenes, methane,carbon dioxide, etc. In one embodiment, the gas-phase separatorcomprises a fractionation column. In one embodiment, acetic acid is sentvia a line 128 to an optional acid hydrogenation unit. In anotherembodiment, methanol and/or furfural are sent via optional additionalline(s) 136 to a distillation/processing unit 138

In various embodiments, as discussed in more detail below, the carbonrecovery unit itself has the facility to enrich the material. In variousother embodiments, the material is enriched in a material enrichmentunit separate from the carbon recovery unit. It should be appreciatedthat, in some such embodiments, the carbon recovery unit is a vessel forstoring the carbonized material, and the separate material enrichmentunit is the unit in which gases are introduced to enrich the material.

In the illustrated embodiment, the carbon recovery unit 500 alsoenriches the carbonized biomass 126. The carbonized biomass 126 exitsthe third reactor along the material transport unit 304 and enters thecarbon recovery unit 500. In various embodiments, as illustrated in moredetail in FIG. 5 and discussed above, the carbon recovery unit 500 alsoincludes an input 524 connected to the gas-phase separator 200. In oneembodiment, the enrichment gas 204 is directed into the carbon recoveryunit to be combined with the biogenic reagent 126 to create a highcarbon biogenic reagent 136. In another embodiment, a carbon-enrichedgas from an external source can also be directed to the carbon recoveryunit to be combined with the carbonized biomass 126 to add additionalcarbon to the ultimate high carbon biogenic reagent produced. In variousembodiments, the carbonized biomass 126 is temperature-reducedcarbonized biomass. Illustratively, the system 100 can be co-locatednear a timber processing facility and carbon-enriched gas from thetimber processing facility can be used as gas from an external source.

Referring now generally to FIG. 2, a block flow diagram of a singlereactor, multi-zone embodiment of the present disclosure is illustrated.In the illustrated embodiment, the raw material 209, such as biomass, isintroduced into the reactor 200 in a low-oxygen atmosphere, optionallythrough the use of a material feed system 108 already described. Asdiscussed in further detail below, the material feed system 108 reducesthe oxygen level in the ambient air in the system to not more than about3%. The raw material 209 enters the BPU 202 in an enclosed materialtransport unit 304 after the oxygen levels have been decreased. In oneembodiment, the material transport unit will include an encapsulatedjacket or sleeve through which steam and off-gases from the reactor 200are sent and used to pre-heat the biomass.

In the illustrated embodiment, the raw material first travels from thematerial feed system 108 on the material transport unit 304 through anoptional drying zone 210 of the BPU 202. In one embodiment, the optionaldrying zone 210 heats the raw material to remove water and othermoisture prior to being passed along to the preheat zone 212. In oneembodiment, the interior of the optional drying zone 210 is heated to atemperature of about ambient temperature to about 150° C. Water 238 orother moisture removed from the raw material 209 can be exhausted, forexample, from the optional drying zone 210. In another embodiment, theoptional drying zone is adapted to allow vapors and steam to beextracted. In another embodiment, vapors and steam from the optionaldrying zone are extracted for optional later use. As discussed below,vapors or steam extracted from the optional drying zone can be used in asuitable waste heat recovery system with the material feed system. Inone embodiment, the vapors and steam used in the material feed systempre-heat the raw materials while oxygen levels are being purged in thematerial feed system. In another embodiment, biomass is dried outside ofthe reactor and the reactor does not comprise a drying zone.

As discussed in more detail below, in one embodiment, the optionaldrying zone 210 is configured to be connected to the cooling zone 216 torecover waste heat 232 and conserve energy through a suitable waste heatrecovery system. In one embodiment, the waste heat given off in thecooling zone 216 is used to operate a heating mechanism configured todry raw materials 209 in the optional drying zone 210. After being driedfor a desired period of time, the dried biomass 221 exits the optionaldrying zone 210 and enters preheat zone 212.

In the illustrated embodiment, the dried biomass 221 enters the first(preheat) zone 212, wherein the temperature is raised from the range ofabout ambient temperature to about 150° C. to a temperature range ofabout 100° C. to about 200° C. In one embodiment, the temperature doesnot exceed 200° C. in the first/preheat zone 212. It should beappreciated that if the preheat zone 212 is too hot or not hot enough,the dried biomass 221 may process incorrectly prior to entering thesecond zone 214. As discussed in greater detail below, the preheat zone212 can includes an output mechanism to capture and exhaust off gas 220from the dried biomass 221 while it is being preheated. In anotherembodiment, the off-gases 220 are extracted for optional later use. Invarious embodiments, the heating source used for the various zones inthe BPU 202 is electric or gas. In one embodiment, the heating sourceused for the various zones of the BPU 202 is waste gas from other zonesof the unit 202 or from external sources. In various embodiments, theheat is indirect.

Following the preheat zone 212, the material transport unit 304 passesthe preheated material 223 into the second (pyrolysis) zone 214. In oneembodiment, the material transport unit 304 penetrates thesecond/pyrolysis zone through a high-temperature vapor seal system (suchas an airlock, not shown), which allows the material transport unit 304to penetrate the high-temperature pyrolysis zone while preventing (orminimizing) gas from escaping. In one embodiment, the interior of thepyrolysis zone 214 is heated to a temperature of about 100° C. to about600° C. or about 200° C. to about 500° C. In another embodiment, thepyrolysis zone 214 includes an output port similar to the preheat zone212 to capture and exhaust the gases 222 given off of the preheatedbiomass 223 while it is being carbonized. In one embodiment, the gases222 are extracted for optional later use. In one illustrativeembodiment, the off-gases 220 from the preheat zone 212 and theoff-gases 222 from the pyrolysis zone 214 are combined into one gasstream 224. Once carbonized, the carbonized biomass 225 exits thesecond/pyrolysis zone 214 and enters the third/temperature reducing orcooling zone 216.

In one embodiment, when the carbonized biomass 225 enters the coolingzone 216, the carbonized biomass 225 is allowed to cool to a specifiedtemperature range of about 20° C. to 25° C. (about room temperature) tobecome temperature-reduced carbonized biomass 226, as discussed above.In various embodiments, the BPU 202 includes a plurality of coolingzones. In one embodiment, the cooling zone 216 cools the carbonizedbiomass to below 200° C. In one embodiment, the cooling zone includes amixer to agitate and uniformly cool the materials. In variousembodiments, one or more of the plurality of cooling zones is outside ofthe BPU 202.

As illustrated in FIGS. 2 and 5, the gas-phase separator unit 200includes at least one input and a plurality of outputs. In thisillustrative embodiment, the at least one input is connected to theexhaust ports on the first/preheat zone 212 and the second/pyrolysiszone 214 of the BPU 202. One of the outputs is connected to the carbonrecovery unit 500 (which is configured to enrich the material), andanother one of the outputs is connected to collection equipment orfurther processing equipment such as an acid hydrogenation unit 206 ordistillation column. In various embodiments, the gas-phase separatorprocesses the off gases 220, 222 from the first/preheat zone 212 and thesecond/pyrolysis zone 214 to produce a condensate 228 and an enrichmentgas 204. In one embodiment, the condensate 228 includes polar compounds,such as acetic acid, methanol and furfural. In one embodiment, theenrichment gas 204 produced by the gas-phase separator 200 includes atleast non-polar gases. In one embodiment, the gas-phase separatorcomprises a fractionation column. In one embodiment, acetic acid is sentvia a line 228 to an optional acid hydrogenation unit 206. In anotherembodiment, methanol and/or furfural are sent via optional additionalline(s) 236 to a distillation/processing unit 238.

In the illustrated embodiments, the carbonized biomass exits the coolingreactor/zone along the material transfer unit 304 and enters the carbonrecovery unit 500. In various embodiments, as illustrated in more detailin FIG. 5 and discussed above, the carbon recovery unit 500 alsoincludes an input 524 connected to the gas-phase separator 200. In oneembodiment, the enrichment gas 204 is directed into the carbon recoveryunit 500 to be combined with the biogenic reagent 226 to create a highcarbon biogenic reagent 136. In another embodiment, a carbon-enrichedgas from an external source can also be directed to the carbon recoveryunit 500 to be combined with the biogenic reagent 226 to add additionalcarbon to the biogenic reagent. In various embodiments, gases pulledfrom the carbon recovery unit 500 at reference 234 are optionally usedin energy recovery systems and/or systems for further carbon enrichment.Similarly, in various embodiments, gases pulled from one or more zonesof the BPU 202 are optionally used in energy recovery systems and/orsystems for further carbon enrichment. Illustratively, the system 200can be co-located near a timber processing facility and carbon-enrichedgas from the timber processing facility can be used as gas from anexternal source.

Now referring generally to FIG. 3, one material feed system embodimentof the present disclosure is illustrated. As discussed above, highoxygen levels in the ambient air surrounding the raw material as itprocesses could result in undesirable combustion or oxidation of the rawmaterial, which reduces the amount and quality of the final product. Inone embodiment, the material feed system is a closed system and includesone or more manifolds configured to purge oxygen from the airsurrounding the raw material. In one embodiment, oxygen level of about0.5% to about 1.0% are used for pre-heating, pyrolyzing/carbonizing andcooling. It should be appreciated that a primary goal of the closedmaterial feed system is to reduce oxygen levels to not more than about3%, not more than about 2%, not more than about 1% or not more thanabout 0.5%. After the oxygen level is reduced, the biomass istransferred along the material feed system into the BPU. It should beappreciated that in various embodiments, pre-heating of inert gasesthrough recovered process energy and subsequent introduction ofpre-heated inert gases to the BPU, reactor or trimming reactor makes thesystem more efficient.

In some embodiments, a trimming reactor is included in the system. Inone trimming reactor embodiment, pyrolyzed material from the BPU is fedinto a separate additional reactor for further pyrolysis where heatedinert gas is introduced to create a product with higher fixed carbonlevels. In various embodiments, the secondary process may be conductedin a container such as a drum, tank, barrel, bin, tote, pipe, sack,press, or roll-off container. In various embodiments, the finalcontainer also may be used for transport of the carbonized biomass. Insome embodiments, the inert gas is heated via a heat exchanger thatderives heat from gases extracted from the BPU and combusted in aprocess gas heater.

As seen in FIG. 3, the closed material feed system 108 includes a rawmaterial feed hopper 300, a material transport unit 304 and an oxygenpurge manifold 302.

In one embodiment, the raw material feed hopper 300 is any suitableopen-air or closed-air container configured to receive raw orsized/dried biomass 109/209. The raw material feed hopper 300 isoperably connected with the material transport unit 304, which, in oneembodiment, is a screw or auger system operably rotated by a drivesource. In one embodiment, the raw material 109/209 is fed into thematerial transport unit 304 by a gravity feed system. It should beappreciated that the material transport unit 304 of FIG. 3 is fashionedsuch that the screw or auger 305 is enclosed in a suitable enclosure307. In one embodiment, the enclosure 307 is substantially cylindricallyshaped. In various embodiments, material feed systems include a screw,auger, conveyor, drum, screen, chute, drop chamber, pneumatic conveyancedevice, including a rotary airlock or a double or triple flap airlock.

As the raw material 109/209 is fed from the raw material feed hopper 300to the material transport unit 304, the auger or screw 305 is rotated,moving the raw material 109/209 toward the oxygen purge manifold 302. Itshould be appreciated that, when the raw material 109/209 reaches theoxygen purge manifold 302, the ambient air among the raw material109/209 in the material transport unit 304 includes about 20.9% oxygen.In various embodiments, the oxygen purge manifold 302 is arrangedadjacent to or around the material transport unit 304. Within the oxygenfold manifold of one embodiment, the enclosure 307 of the materialtransport unit 304 includes a plurality of gas inlet ports 310 a, 310 b,310 c and a plurality of gas outlet ports 308 a, 308 b, 308 c.

The oxygen purge manifold 302 has at least one gas inlet line 312 and atleast one gas outlet line 314. In various embodiments, the at least onegas inlet line 312 of the oxygen purge manifold 302 is in operablecommunication with each of the plurality of gas inlet ports 310 a, 310b, 310 c. Similarly, in various embodiments, the at least one gas outletline 314 of the oxygen purge manifold 302 is in operable communicationwith each of the plurality of gas outlet ports 308 a, 308 b, 308 c. Itshould be appreciated that, in one embodiment, the gas inlet line 312 isconfigured to pump an inert gas into the gas inlet ports 310 a, 310 b,310 c. In one such embodiment, the inert gas is nitrogen containingsubstantially no oxygen. In one embodiment, the inert gas will flowcounter-current to the biomass.

As will be understood, the introduction of inert gas 312 into theenclosed material transport unit 304 will force the ambient air out ofthe enclosed system. In operation, when the inert gas 312 is introducedto the first gas inlet port 310 a of one embodiment, a quantity ofoxygen-rich ambient air is forced out of outlet port 308 a. It should beappreciated that, at this point, the desired level of not more thanabout 2% oxygen, not more than about 1% oxygen, not more than about 0.5%oxygen or not more than about 0.2% oxygen may not be achieved.Therefore, in various embodiments, additional infusions of the inert gas312 must be made to purge the requisite amount of oxygen from the airsurrounding the raw material 109 in the enclosed system. In oneembodiment, the second gas inlet port 310 b pumps the inert gas 312 intothe enclosed system subsequent to the infusion at the first gas inletport 310 a, thereby purging more of the remaining oxygen from theenclosed system. It should be appreciated that, after one or twoinfusions of inert gas 312 to purge the oxygen 314, the desired level ofless oxygen may be achieved. If, in one embodiment, the desired oxygenlevels are still not achieved after two inert gas infusions, a thirdinfusion of inert gas 312 at gas inlet 310 c will purge remainingundesired amounts of oxygen 314 from the enclosed system at gas outlet308 c. Additional inlets/outlets may also be incorporated if desired. Invarious embodiments, oxygen levels are monitored throughout the materialfeed system to allow calibration of the amount and location of inert gasinfusions.

In one alternative embodiment, heat, steam and gases recovered from thereactor are directed to the feed system where they are enclosed injacket and separated from direct contact with the feed material, butindirectly heat the feed material prior to introduction to the reactor.

In one alternative embodiment, heat, steam and gases recovered from thedrying zone of the reactor are directed to the feed system where theyare enclosed in jacket and separated from direct contact with the feedmaterial, but indirectly heat the feed material prior to introduction tothe reactor.

It should be appreciated that the gas inlet ports 310 a, 310 b, 310 cand the corresponding gas outlet ports 308 a, 308 b, 308 c,respectively, of one embodiment are slightly offset from one anotherwith respect to a vertical bisecting plane through the materialtransport unit 304. For example, in one embodiment, inlet port 310 a andcorresponding outlet port 308 a are offset on material transport unit304 by an amount that approximately corresponds with the pitch of theauger 305 in the material transport unit 304. In various embodiments,after the atmosphere surrounding the raw material 109/209 issatisfactorily de-oxygenated, it is fed from the material feed system108 into the BPU 102. In various embodiments, oxygen levels aremonitored throughout the material feed system to allow the calibrationof the amount and location of inert gas infusions.

It should be appreciated that, in one embodiment, the raw material109/209, and subsequently the dried biomass 221, preheated biomass123/223, carbonized biomass 125/225 and carbonized biomass 126/226,travel through the reactor 102 (or reactors) along a continuous materialtransport unit 304. In another embodiment, the material transport unitcarrying the material differs at different stages in the process. In oneembodiment, the process of moving the material through the reactor,zones or reactors is continuous. In one such embodiment, the speed ofthe material transport unit 304 is appropriately calibrated andcalculated by an associated controller and processor such that theoperation of the material transport unit 304 does not requireinterruption as the material moves through the reactor or reactors.

In another embodiment, the controller associated with the reactor 102 orreactors (112/114/116) is configured to adjust the speed of the materialtransport unit 304 based on one or more feedback sensors, detected gas(e.g. from the optional FTIR), measured parameters, temperature gauges,or other suitable variables in the reactor process. It should beappreciated that, in various embodiments, any suitable moisture sensors,temperature sensors or gas sensors in operable communication with thecontroller and processor could be integrated into or between each of thezones/reactors or at any suitable position along the material transportunit 304. In one embodiment, the controller and processor use theinformation from sensors or gauges to optimize the speed and efficiencyof the BPU 100/200. In one embodiment, the controller associated withthe reactor 102 or reactors (112/114/116) is configured to operate thematerial transport unit 304. In one embodiment, the controllerassociated with the reactor 102 or reactors (112/114/116) is configuredto monitor the concentration, temperature and moisture of the gas insidethe material transport unit 304 or inside any of the reactors. In oneembodiment, the controller is configured to adjust the speed of thematerial transport unit 304, the input of gases into the materialtransport unit and the heat applied to the material in the materialtransport unit based upon one or more readings taken by the varioussensors.

Referring now to FIGS. 2 and 4, one embodiment of the BPU 102 isillustrated. It should be appreciated that the graphical representationof the BPU 202 in FIG. 4 corresponds substantially to the BPU 202 inFIG. 2. It should also be appreciated that, in various embodiments, theBPU 202 is enclosed in a kiln shell to control and manipulate the highamounts of heat required for the reactor process. As seen in FIG. 4, inone embodiment, the kiln shell of the BPU 202 includes severalinsulating chambers (416, 418) surrounding the four zones 210, 212, 214and 216. In one embodiment, the kiln includes four separated zones. Invarious embodiments, each of the four zones 210, 212, 214 and 216 of theBPU 202 includes at least one inlet flight and at least one outletflight. As discussed in greater detail below, within each zone of onesuch embodiment, the inlet and outlet flights are configured to beadjustable to control the flow of feed material, gas and heat into andout of the zone. A supply of inert air can be introduced into the inletflight and the purged air can be extracted from the corresponding outletflight. In various embodiments, one or more of the outlet flights of azone in the BPU 202 are connected to one or more of the other inlet oroutlet flights in the BPU.

In one embodiment, after the raw material 209 is de-oxygenated in thematerial feed system 108, it is introduced to the BPU 202, andspecifically to the first of four zones the optional drying zone 210. Asseen in FIG. 4, the drying zone includes inlet flight 422 b and outletflight 420 a. In one embodiment, the drying zone is heated to atemperature of about 80° C. to about 150° C. to remove water or othermoisture from the raw materials 209. The biomass is then moved to thesecond or pre-heat zone 212 where the biomass is pre-heated as describedabove.

In another embodiment, the material that has optionally been dried andpre-heated is moved to the third or carbonization zone. In oneembodiment, carbonization occurs at a temperature from about 200° C. toabout 700° C., for example about 200° C., about 210° C., about 220° C.,about 230° C., about 240° C., about 250° C., about 260° C., about 270°C., about 280° C., about 290° C., about 300° C., about 310° C., about320° C., about 330° C., about 340° C., about 350° C., about 360° C.,about 370° C., about 380° C., about 390° C., about 400° C., 410° C.,about 420° C., about 430° C., about 440° C., about 450° C., about 460°C., about 470° C., about 480° C., about 490° C., about 500° C., about510° C., about 520° C., about 530° C., about 540° C., about 550° C.,about 560° C., about 570° C., about 580° C., about 590° C., about 600°C., about 610° C., about 620° C., about 630° C., about 640° C., about650° C., about 660° C., about 670° C., about 680° C., about 690° C., orabout 700° C. In another embodiment, a carbonization zone of a reactor421 is adapted to allow gases produced during carbonization to beextracted. In another embodiment, gases produced during carbonizationare extracted for optional later use. In one embodiment, a carbonizationtemperature is selected to minimize or eliminate production of methane(CH₄) and maximize carbon content of the carbonized biomass.

In another embodiment, carbonized biomass is moved to a temperaturereducing or cooling zone (third zone) and is allowed to passively coolor is actively cooled. In one embodiment, carbonized biomass solids arecooled to a temperature ±10, 20, 30 or 40° C. of room temperature.

In various embodiments, the BPU includes a plurality of gas introductionprobes and gas extraction probes. In the embodiment of the BPUillustrated in FIG. 4, the BPU further includes a plurality of gasintroduction probes: 408, 410, 412 and 414, and a plurality of gasextraction probes: 400, 402, 404 and 406. It should be appreciated that,in various embodiments, one of each gas introduction probes and one ofeach gas extraction probes correspond with a different one of theplurality of zones 210, 212, 214 and 216. It should also be appreciatedthat, in various alternative embodiments, the BPU 202 includes anysuitable number of gas introduction probes and gas extraction probes,including more than one gas introduction probes and more than one gasextraction probes for each of the plurality of zones.

In the illustrated embodiment, the drying zone 210 is associated withgas introduction probe 412 and gas extraction probe 402. In oneembodiment, the gas introduction probe 412 introduces nitrogen to thedrying zone 210 and the gas extraction probe 402 extracts gas from thedrying zone 210. It should be appreciated that, in various embodiments,the gas introduction probe 412 is configured to introduce a mixture ofgas into the drying zone 210. In one embodiment, the gas extracted isoxygen. It should be appreciated that, in various embodiments, the gasextraction probe 402 extracts gases from the drying zone 210 to bereused in a heat or energy recovery system, as described in more detailabove.

In the illustrated embodiment, the pre-heat zone 212 is associated withgas introduction probe 414 and gas extraction probe 400. In oneembodiment, gas introduction probe 414 introduces nitrogen to thepre-heat zone 212 and gas extraction probe 400 extracts gas from thepre-heat zone 212. It should be appreciated that, in variousembodiments, the gas introduction probe 414 is configured to introduce amixture of gas into the pre-heat zone 212. In various embodiments, thegas extracted in gas extraction probe 400 includes carbon-enrichedoff-gases. It should be appreciated that in one embodiment, as discussedabove, the gases extracted from the pre-heat zone 212 and pyrolysis zone214 are reintroduced to the material at a later stage in the process,for example in the carbon recovery unit. In various embodiments, thegases extracted from any of the zones of the reactor are used for eitherenergy recovery in the dryer or process gas heater, for furtherpyrolysis in a trimming reactor, or in the carbon enrichment unit.

In the illustrated embodiment, the pyrolysis zone 214 is associated withgas introduction probe 410 and gas extraction probe 404. In oneembodiment, gas introduction probe 410 introduces nitrogen to thepyrolysis zone 214 and gas extraction probe 404 extracts gas from thepyrolysis zone 214. It should be appreciated that, in variousembodiments, the gas introduction probe 410 is configured to introduce amixture of gas into the pyrolysis zone 214. In various embodiments, thegas extracted in the gas extraction probe 404 includes carbon-enrichedoff-gases. It should be appreciated that in one embodiment, as discussedabove, the carbon-enriched gases extracted from the pyrolysis zone 214are used and reintroduced to the material at a later stage in theprocess. In various embodiments, as described in more detail below, theextracted gas 400 from the pre-heat zone 212 and the extracted gas 404from the pyrolysis zone 214 are combined prior to being reintroduced tothe material.

In the illustrated embodiment, the cooling zone 116 is associated withgas introduction probe 408 and gas extraction probe 406. In oneembodiment, gas introduction probe 408 introduces nitrogen to thecooling zone 116 and gas extraction probe 406 extracts gas from thecooling zone 116. It should be appreciated that, in various embodiments,the gas introduction probe 408 is configured to introduce a mixture ofgas into the cooling zone 116. It should be appreciated that, in variousembodiments, the gas extraction probe 406 extracts gases from thecooling zone 116 to be reused in a heat or energy recovery system, asdescribed in more detail above.

It should be appreciated that the gas introduction probes and gasextraction probes of various embodiments described above are configuredto operate with the controller and plurality of sensors discussed aboveto adjust the levels and concentrations of gas being introduced to andgas being extracted from each zone.

In various embodiments, the gas introduction probes and gas extractionprobes are made of a suitable pipe configured to withstand hightemperature fluctuations. In one embodiment, the gas introduction probesand gas extraction probes include a plurality of openings through whichthe gas is introduced or extracted. In various embodiments, theplurality of openings is disposed on the lower side of the inlet and gasextraction probes. In various embodiments, each of the plurality ofopenings extends for a substantial length within the respective zone.

In one embodiment, the gas introduction probes extend from one side ofthe BPU 202 through each zone. In one such embodiment, each of the fourgas introduction probes extend from a single side of the BPU to each ofthe respective zones. In various embodiments, gaseous catalysts areadded that enrich fixed carbon levels. It should be appreciated that, insuch an embodiment, the plurality of openings for each of the four gasintroduction probes are only disposed in the respective zone associatedwith that particular gas introduction probe.

For example, viewing FIG. 4, if each of the gas introduction probesextends from the left side of the drying zone into each one of thezones, all four gas introduction probes would travel through the dryingzone, with the drying zone gas introduction probes terminating in thedrying zone. The three remaining gas introduction probes would alltravel through the pre-heat zone, with the pre-heat zone gasintroduction probe terminating in the pre-heat zone. The two remaininggas introduction probes would travel through the pyrolysis zone, withthe pyrolysis zone gas introduction probe terminating in the pyrolysiszone. The cooling zone gas introduction probe would be the only gasintroduction probe to travel into and terminate in the cooling zone. Itshould be appreciated that in various embodiments, the gas extractionprobes are configured similar to the gas introduction probes describedin this example. It should also be appreciated that the gas introductionprobes and gas extraction probes can each start from either side of theBPU.

In various embodiment, the gas introduction probes are arrangedconcentrically with one another to save space used by the multiple-portconfiguration described in the example above. In one such embodiment,each of the four inlet probes/ports would have a smaller diameter thanthe previous inlet probe/port. For example, in one embodiment, thedrying zone gas introduction probe has the largest interior diameter,and the pre-heat zone gas introduction probe is situated within theinterior diameter of the drying zone inlet probe/port, the pyrolysiszone gas introduction probe is then situated within the interiordiameter of the pre-heat zone gas introduction probe and the coolingzone gas introduction probe is situated within the pyrolysis zone gasintroduction probe. In one example embodiment, a suitable connector isattached to each of the four gas introduction probes outside of the BPU102 to control the air infused into each of the four gas introductionprobes individually.

In one such embodiment, similar to the example above, the drying zonegas introduction probe would terminate in the drying zone, and the threeother gas introduction probes would continue onto the preheat zone.However, with a concentric or substantially concentric arrangement, onlythe outer-most gas introduction probe is exposed in each zone beforebeing terminated. Therefore, in one such embodiment, the individual zonegas introductions are effectively controlled independent of one another,while only requiring one continuous gas introduction probe line. Itshould be appreciated that a similar concentric or substantiallyconcentric configuration is suitably used for the gas extraction probesin one embodiment.

In one embodiment, each zone or reactor is adapted to extract andcollect off-gases from one or more of the individual zones or reactors.In another embodiment, off-gases from each zone/reactor remain separatefor disposal, analysis and/or later use. In various embodiments, eachreactor/zone contains a gas detection system such as an FTIR that canmonitor gas formation within the zone/reactor. In another embodiment,off-gases from a plurality of zones/reactors are combined for disposal,analysis and/or later use, and in various embodiments, off gases fromone or more zones/reactors are fed to a process gas heater. In anotherembodiment, off-gases from one or more zones/reactors are fed into acarbon recovery unit. In another embodiment, off-gases from one or morezones/reactors are fed to a gas-phase separator prior to introduction inthe carbon recovery unit. In one embodiment, a gas-phase separatorcomprises a fractionation column. Any fractionation column known tothose skilled in the art may be used. In one embodiment, off-gases areseparated into non-polar compounds and polar compounds using a standardfractionation column heated to a suitable temperature, or a packedcolumn. In another embodiment, non-polar compounds or enriched gasesfrom a gas-phase separator are extracted for optional later use, and invarious embodiments, off gases from one or more zones/reactors are fedto a process gas heater. In one embodiment, gases extracted from thepre-heat zone/reactor, the pyrolysis zone/reactor and optionally thecooling zone/reactor are extracted into a combined stream and fed intothe gas-phase separator. In various embodiments, one or more of thezones/reactors is configured to control whether and how much gas isintroduced into the combined stream.

As discussed above and generally illustrated in FIG. 5, the off-gases124/224 from the BPU 102/202 are directed into the gas-phase separator200. In various embodiments, the off-gases 124/224 include the extractedgases 120 from the first/preheat zone/reactor 112/212 combined with theextracted gases 122/222 from the second/pyrolysis zone/reactor 114/214or either gas stream alone. When the off-gases 124/224 enter thegas-phase separator 200, the off-gases 124/224 are separated into polarcompounds 128/228/136/236 and non-polar compounds 204, such as non-polargases. In various embodiments, the gas-phase separator 200 is a knownfractionation column.

In various embodiments, the enriched gases 204 extracted from thecombined off-gases 124/224 are directed from the gas-phase separator 200into the carbon recovery unit 500 via input 524, which enriches thematerial. As discussed above, and as illustrated in FIGS. 8 and 11, itshould be appreciated that in various embodiments, the extracted gasesare first introduced into a material enrichment unit, and then into aseparate carbon recovery unit. In the embodiment illustrated in FIG. 5,the material enrichment takes place in the carbon recovery unit 500. Inone embodiment (FIG. 5), the gas-phase separator 200 includes aplurality of outputs. In various embodiments, one output from thegas-phase separator 200 is connected to the carbon recovery unit 500 tointroduce an enriched gas stream to the carbon recovery unit 500. In oneembodiment, a portion of the enriched gas stream is directed to thecarbon recovery unit 500 and another portion is directed to a scrubber,or another suitable purifying apparatus to clean and dispose of unwantedgas. In various embodiments, off-gases that are not sent to the carbonrecovery unit may be used for either energy recovery (for example in aprocess gas heater) or as an inert gas (for example in the deaerationunit, reactor, BPU, or cooler). Similarly, in various embodiments,off-gases from the carbon recovery unit may be used for either energyrecovery (for example in a process gas heater), as an inert gas (forexample in the deaeration unit, reactor, BPU, or cooler), or in asecondary recovery unit.

In one embodiment, another output from the gas-phase separator extractspolar compounds, optionally condensing them into a liquid component,including a plurality of different liquid parts. In various embodiments,the liquid includes water, acetic acid, methanol and furfural. Invarious embodiments, the outputted liquid is stored, disposed of,further processed, or re-used. For example, it should be appreciatedthat the water outputted in one embodiment can be re-used to heat orcool another portion of a system. In another embodiment, the water isdrained. It should also be appreciated that the acetic acid, methanoland furfural outputted in one embodiment can be routed to storage tanksfor re-use, re-sale, distillation or refinement.

As seen in FIG. 5, the carbon recovery unit 500 of one embodimentcomprises a housing with an upper portion and a lower portion. It shouldbe appreciated that, in various embodiments in which a materialenrichment unit is separate from the carbon recovery unit, the materialenrichment unit includes features similar to those discussed withrespect to the carbon recovery unit 500 of FIG. 5. In one embodiment,the carbon recovery unit, comprises: a housing 502 with an upper portion502 a and a lower portion 502 b; an inlet 524 at a bottom of the lowerportion of the housing configured to carry reactor off-gas; an outlet534 at a top of the upper portion of the housing configured to carry aconcentrated gas stream; a path 504 defined between the upper portionand lower portion of the housing; and a transport system 528 followingthe path, the transport system configured to transport reagent, whereinthe housing is shaped such that the reagent adsorbs at least some of thereactor off-gas. In various embodiments, the upper portion includes aplurality of outlets and the lower portion includes a plurality ofinlets.

In one embodiment, the housing 502 is substantially free of cornershaving an angle of 110 degrees or less, 90 degrees or less, 80 degreesor less or 70 degrees or less. In one embodiment, the housing 502 issubstantially free of convex corners. In another embodiment, the housing502 is substantially free of convex corners capable of producing eddiesor trapping air. In another embodiment, the housing 502 is substantiallyshaped like a cube, rectangular prism, ellipsoid, a stereographicellipsoid, a spheroid, two cones affixed base-to-base, two regulartetrahedrons affixed base-to-base, two rectangular pyramids affixedbase-to-base or two isosceles triangular prisms affixed base-to-base.

In one embodiment, the upper portion 502 a and lower portion 502 b ofthe housing 502 are each substantially shaped like a half-ellipsoid,half rectangular prism, half-stereographic ellipsoid, a half-spheroid, acone, a regular tetrahedron, a rectangular pyramid, an isoscelestriangular prism or a round-to-rectangular duct transition.

In another embodiment, the inlet 524 at the bottom of the lower portionof the housing 502 b and the outlet 534 at the top of the upper portionof the housing 502 a are configured to connect with a pipe. In anotherembodiment, the top of the lower portion of the housing 502 b and thebottom of the upper portion of the housing 502 a are substantiallyrectangular, circular or elliptical. In another embodiment, the widthbetween the top of the lower portion of the housing 502 b and the bottomof the upper portion of the housing 502 a is wider than a width of thetransport system 528. In one embodiment, the width of the transportsystem 528 is its height.

In one embodiment, the carbon recovery unit 500 comprises a path 504defined between the upper portion and the lower portion, an inletopening 506 and an outlet opening 508. In one embodiment, the inletopening, and outlet opening are configured to receive the transportsystem. In one embodiment, the transport system 528 is at leastsemi-permeable or permeable to the enriching gas.

In one embodiment, the inlet opening 506 includes an inlet openingsealing mechanism to reduce escape of gas and the outlet opening 508includes an outlet opening sealing mechanism to reduce escape of gas. Inone embodiment, the inlet and outlet opening sealing mechanisms comprisean airlock.

In various embodiments, the lower portion 502 b of the housing of thecarbon recovery unit has a narrow round bottom connection opening, whichis connected to the gas phase separator 200 for the transport of gasstream 204. In various embodiments, the top of the lower portion 502 bof the housing of the carbon recovery unit 500 is substantiallyrectangular in shape, and substantially wider than the narrow roundbottom connection opening. It should be appreciated that in oneembodiment, the lower portion transitions from the round bottom openingto a rectangular top opening. In one embodiment, the rectangular topopening of the lower portion is about six feet wide (along the directionof the conveyor system). In various embodiments, the top portion of thecarbon recovery unit 500 is shaped substantially similarly to the lowerportion. In one embodiment, the lower opening of the top portion iswider than the top opening of the lower portion. In one embodiment, therectangular lower opening of the top portion is about six and a halffeet wide (along the direction of the conveyor system). In oneembodiment, the top portion is configured to capture all gases passedthrough the carbon recovery unit 500 that are not adsorbed by the porousmaterials.

It should be appreciated that, in various embodiments, the shape of thelower portion of the carbon recovery unit aids in slowing down anddispersing the gases 204 across a wider surface area of the conveyorcarrying the biogenic reagent 126/226. In various embodiments, theprecise shape of the lower 502 b and upper 502 a portions of the carbonrecovery unit 500 depend upon the angle of gas dispersion coming fromthe gas-phase separator pipe. It should be appreciated that in variousembodiments, the gas naturally will tend to expand as it is pumped up ata flared range of between 5 and 30 degrees from the vertical. In oneembodiment, the flare angle is approximately 15 degrees. It should beappreciated that the lower portion of the carbon recovery unit isconstructed with as few creases and corners as possible to prevent thetrapping of air or formation of eddies.

In one embodiment, the carbon recovery unit 500 is configured to connectto the gas-phase separator 200 as discussed above, as well as the BPU102/202. In various embodiments, the carbon recovery unit 500 isconnected to the output of the cooling reactor/zone 216/116, or the lastcooling zone of the BPU 102/202 or outside of the BPU. In oneembodiment, the output of the cooling reactor/zone 116/216 includesbiogenic reagent that have been processed in the BPU 102/202. In oneembodiment, the biogenic reagent 126/226 enter the carbon recovery unit500 along a suitable transport system. In various embodiments, the topportion and the bottom portion of the carbon recovery unit are connectedto one another and define a pathway through which a transport systempasses. In one embodiment, the transport system is constructed with aporous or mesh material configured to allow gas to pass there through.It should be appreciated that the transport system is configured to passthrough an opening of the carbon recovery unit 500 and then through anexit opening in the carbon recovery. In some embodiments, the entranceand the exit into and out of the carbon recovery unit are appropriatelysealed with an airlock or another suitable sealing mechanism to preventgases from escaping through the conveyor opening. In variousembodiments, off-gases that are not sent to the carbon recovery unit maybe used for either energy recovery (for example in a process gas heater)or as an inert gas (for example in the deaeration unit, reactor, BPU, orcooler). Similarly, in various embodiments, off-gases from the carbonrecovery unit may be used for either energy recovery (for example in aprocess gas heater), as an inert gas (for example in the deaerationunit, reactor, BPU, or cooler), or in a secondary recovery unit.

In various embodiments, the process operates by first outputting thebiogenic reagent 126/226 from the cooling zone 116/216 onto thetransport system using a suitable discharge mechanism from the coolingreactor/zone 116/216. In one embodiment, the biogenic reagent 126/216are spread across the width of the transport system to minimize materialstacking or bunching and maximize surface area for gaseous absorption.At the point which the biogenic reagent 126/216 are deposited andsuitably spread onto the transport system, in various embodiments, thetransport system transports the biogenic reagent 126/216 through theopening in the carbon recovery unit 104 defined between the lowerportion and the top portion discussed above. In the carbon recovery unit104, the biogenic reagent 126/216 adsorb gases piped into the lowerportion of the carbon recovery unit 104 from the gas-phase separator200. After the biogenic reagent is enriched with non-polar gases, itshould be appreciated that the biogenic reagent becomes a high carbonbiogenic reagent. In various embodiments, the high carbon biogenicreagent is a final product of the process disclosed herein and istransported away from the carbon recovery unit 104 into a suitablestorage or post-processing apparatus.

In one embodiment, after the enriched gases 204 pass through theconveyor and the biogenic reagent 126/216, the resulting gas isextracted at the top portion of the carbon recovery unit 104. In variousembodiments, the exhausted gases 134 are carried away to a suitablescrubber, stack or recovery system. In some embodiments, the exhaustgases are exploited for any reusable qualities in the system, includingusage in a secondary carbon recovery unit or for energy. In variousembodiments, off-gases that are not sent to the carbon recovery unit maybe used for either energy recovery (for example in a process gas heater)or as an inert gas (for example in the deaeration unit, reactor, BPU, orcooler). Similarly, in various embodiments, off-gases from the carbonrecovery unit may be used for either energy recovery (for example in aprocess gas heater), as an inert gas (for example in the deaerationunit, reactor, BPU, or cooler), or in a secondary recovery unit.

It should be appreciated that the biogenic reagent 126/216 include ahigh amount of carbon, and carbon has a high preference for adsorbingnon-polar gases. It should also be appreciated that the enriched gasstream 204 includes primarily non-polar gases like terpenes, carbonmonoxide, carbon dioxide and methane. In various embodiments, as theenriched gases are directed from the gas-phase separator into the carbonrecovery unit, the gas flow rate and the conveyor speed are monitoredand controlled to ensure maximum absorption of the non-polar gases inthe biogenic reagent 126/216. In another embodiment, the high-energyorganic compounds comprise at least a portion of the enriched gases 204eluted during carbonization of the biomass and outputted from thegas-phase separator 200 to the carbon recovery unit 104. In variousembodiments, the enriched gases 204 are further enriched with additionaladditives prior to being introduced to the carbon recovery unit ormaterial enrichment unit.

As discussed in more detail below, in various embodiments, the residencetime of the biogenic reagent 126/216 in the carbon recovery unit iscontrolled and varies based upon the composition of the biogenic reagent126/216 and gas flow and composition. In one embodiment, the biogenicreagent is passed through one or more carbon recovery units more thanone time. In various embodiments, the output of enriched air from thegas-phase separator and the output of exhausted air from the carbonrecovery unit 104 can be diverted or bifurcated into an additionalcarbon recovery unit or further refined or used for energy or inert gasfor use in the process.

Referring more generally to FIGS. 6 to 13, various embodiments of thepresent disclosure are illustrated and discussed. It should beappreciated that the various embodiments and alternatives discussedbelow with respect to FIGS. 6 to 13 apply to the embodiments of FIGS. 1to 5 discussed above, and vice versa.

Referring specifically now to FIG. 6, this embodiment can utilize a BPUincluding a single reactor having two to a greater plurality ofdifferent zones. Two zones are shown in the illustrative embodiment;however, any different number of zones could be employed. In oneembodiment, each zone is connected to at least one other zone via amaterial transport unit (not pictured). In one embodiment, the materialtransport unit controls atmosphere and temperature conditions.

Specifically, in one embodiment illustrated in FIG. 6, the system 600includes a material feed system 602, a BPU 606 including a pyrolysiszone 608 and a cooling zone 610, a cooler 614 and a carbon recovery unit616. It should be appreciated that the cooler 614 of FIG. 6 is outsideof the BPU 606 and is in addition to the cooling zone 610 that resideswithin the BPU 606.

In various embodiments, the system 600 includes an optional dryerbetween the material feed system 602 and the BPU 606. In variousembodiments, the BPU 606 includes a plurality of zones. In FIG. 6, theBPU 606 includes a pyrolysis zone 608 and a cooling zone 610. The BPU606 also includes at least a plurality of inlets and outlets for addingsubstances to and removing various substances from the plurality of zone608, 610, including at least condensable vapors and non-condensablegases 612. It should be appreciated that in various embodimentsdiscussed below, one or more of the pluralities of zone 608 or 610 areenclosed by the BPU 606.

Referring now to FIG. 7, a system 700 of one embodiment is illustratedand discussed. System 700 includes a single-reactor system, including amaterial feed system 702, a pre-heater 706, a pyrolysis reactor 708, acooler, 714 and a carbon recovery unit 716. In various embodiments, thesystem 700 includes an optional dryer 704 between the material feedsystem 702 and the pre-heater 706. As seen in FIG. 7, the pyrolysisreactor 708 of one embodiment includes at least one gas inlet 710 and atleast one outlet 712 for outputting substances from the pyrolysisreactor 708. In various embodiments, the substances outputted throughoutlet 712 include condensable vapors and/or non-condensable gases. Itshould be appreciated that the pyrolysis reactor 708 can include one ormore zones, not discussed in detail herein. In various embodiments, thesystem 700 includes one or more reactors in addition to the pyrolysisreactor 708.

Referring now to FIG. 8, a single-reactor, multiple zone BPU system 800of one embodiment is illustrated and discussed. System 800 includes amaterial feed system 802, a BPU 808 having a pyrolysis zone 810 and acooling zone 812, a material enrichment unit 818, and a carbon recoveryunit 820. Similar to the embodiments discussed above, FIG. 8 alsoincludes an optional dryer 804 located between the material feed system802 and the BPU 808. It should be appreciated that moisture 806 from thedryer 804 is removed during the drying process. FIG. 8 also includes anoptional cooler 816 outside of the BPU 808 and before the materialenrichment unit 818. As discussed in more detail below, the materialenrichment unit 818 is in communication with a gas outlet 814 of the BPU808, which carries condensable vapors and non-condensable gases from theBPU. It should be appreciated that various embodiments illustrated inFIG. 8 include a separate carbon recovery unit 820 from the materialenrichment unit 818. As discussed above, in various embodiments, thecarbon recovery unit 820 of FIG. 8 is an appropriate vessel in which theenriched material is stored following the material enrichment unit 818,and the carbon recovery unit 820 does not further enrich the material.

It should be appreciated that, in various embodiments, an optionalprocess gas heater 824 is disposed in the system and attached to the BPU808. In various embodiments, vapors or other off-gases from the BPU 808are inputted into the optional process gas heater 824, along with anexternal source of any one or more of air, natural gas, and nitrogen. Asdiscussed below, in various embodiments, the air emissions from theprocess gas heater 824 are inputted into dryer 804 as a heat or energyrecovery system.

Referring now to FIG. 9, a BPU 908 of a system 900 of one embodiment isillustrated and discussed. The BPU 908 includes a plurality of zones:the pre-heat zone 904, the pyrolysis zone 910, and the cooling zone 914.The BPU 908 of one embodiment also includes a material feed system 902in communication with one of the zones at least one gas inlet 906 incommunication with one or more of the zones 904, 910, 914. In variousembodiments, as discussed below, one of the zones also includes at leastone outlet 912 for outputting substances, in one embodiment, condensablevapors and/or non-condensable gases. In various embodiments, one of thezones also includes an outlet for outputting the advanced carbon fromthe system 900.

It should be appreciated that, although FIG. 9 shows the gas inlet 906being connected to the pre-heat zone 904, various embodiments includeinlets into any combination of the three zones. Similarly, it should beappreciated that although the gaseous outlet 912 comes from thepyrolysis zone 910, various embodiments include outlets out of one ormore of any combination of the three zones. As discussed below, variousembodiments contemplated include inputs and outputs within the BPU:e.g., an outlet of the pyrolysis zone 910 is then input into thepre-heat zone 904. It should be appreciated that, in the illustratedembodiment, each of the reactors in the BPU is connected to one anothervia the material feed system, as discussed above.

In various embodiments, the pre-heat zone 904 of the BPU 908 isconfigured for feeding biomass 902 (or another carbon-containingfeedstock) in a manner that does not “shock” the biomass, which wouldrupture the cell walls and initiate fast decomposition of the solidphase into vapors and gases. In one embodiment, pre-heat zone 904 can bethought of as mild pyrolysis.

In various embodiments, pyrolysis zone 910 of the BPU 908 is configuredas the primary reaction zone, in which preheated material undergoespyrolysis chemistry to release gases and condensable vapors, resultingin a solid material which is a high-carbon reaction intermediate.Biomass components (primarily cellulose, hemicellulose, and lignin)decompose and create vapors, which escape by penetrating through poresor creating new nanopores. The latter effect contributes to the creationof porosity and surface area.

In various embodiments, the cooling zone 914 of the BPU 908 isconfigured for receiving the high-carbon reaction intermediate andcooling down the solids, i.e. the cooling zone 914 will be a lowertemperature than the pyrolysis zone 910. In the cooling zone 914, thechemistry and mass transport can be complex. In various embodiments,secondary reactions occur in the cooling zone 914. It should beappreciated that carbon-containing components that are in the gas phasecan decompose to form additional fixed carbon and/or become adsorbedonto the carbon. Thus, the advanced carbon 916 is not simply the solid,devolatilized residue of the processing steps, but rather includesadditional carbon that has been deposited from the gas phase, such as bydecomposition of organic vapors (e.g., tars) that can form carbon.

Referring now to FIGS. 10 to 13, various multiple reactor embodiments ofthe system are illustrated and discussed. Similar to each of theembodiments, the systems include an optional deaerator and an optionaldryer, as discussed in more detail below. Referring to FIG. 10, thesystem 1000 includes material feed system 1002, a pyrolysis reactor1012, a cooling reactor 1018, a cooler 1020 and a carbon recovery unit1022. As discussed further below, a gas source 1016 is configured toinput gas into one or both of the pyrolysis reactor 1012 and the coolingreactor 1018. In various embodiments, the pyrolysis reactor includes anoutlet to output at least condensable vapors and/or non-condensablegases. In various embodiments, the carbon recovery unit 1022 includes anoutlet 1024 to output porous carbon from the system 1000.

It should be appreciated that, in various embodiments illustrated atleast in FIGS. 10 to 13, the illustrated systems include an optionalde-aerator and an optional dryer. As seen in FIG. 10, for example,represented by broken lines, the optional de-aerator 1004 is connectedto the system 1000 between the material feed system 1002 and thepyrolysis reactor 1002. Similarly, the dryer 1006 is connected to thesystem 1000 between the material feed system 1002 and the pyrolysisreactor 1012. In various embodiments, the dryer 1006 and deaerator 1004are also connected to one another such that the material from thematerial feed system can follow any number of different paths throughthe material feed system, the de-aerator, the dryer, and to thepyrolysis reactor. It should be appreciated that in some embodiments,the material only passes through one of the optional de-aerator 1004 anddryer 1006.

In some embodiments, with reference to FIG. 10, a process for producinga high-carbon biogenic reagent comprises the following steps: providinga carbon-containing feedstock comprising biomass; optionally drying thefeedstock to remove at least a portion of moisture contained within thefeedstock; optionally deaerating the feedstock to remove at least aportion of interstitial oxygen, if any, contained with the feedstock;pyrolyzing the feedstock in the presence of a substantially inert gasphase for at least about 10 minutes and with at least one temperatureselected from about 250° C. to about 700° C., to generate hot pyrolyzedsolids, condensable vapors, and non-condensable gases; separating atleast a portion of the condensable vapors and at least a portion of thenon-condensable gases from the hot pyrolyzed solids; cooling the hotpyrolyzed solids to generate cooled pyrolyzed solids; and recovering ahigh-carbon biogenic reagent comprising at least a portion of the cooledpyrolyzed solids.

Referring now to FIG. 11 a multiple reactor system 1100 of oneembodiment is illustrated. Similar to the embodiment discussed above andillustrated in FIG. 10, this embodiment includes a material feed system1102, pyrolysis reactor 1112, cooling reactor 1118, and carbon recoveryunit 1124. In the illustrated embodiment of FIG. 11, the cooler 1120 isoptional, and a material enrichment unit 1122 is disposed between theoptional cooler 1120 and the carbon recovery unit 1124. It should beappreciated that, in various embodiments, the material enrichment unit1122 enriches the material before it continues into the separate carbonrecovery unit 1124, which may or may not further enrich the material. Invarious embodiments, an optional deaerator 1104 and an optional dryer1106 are disposed between the material feed system 1102 and thepyrolysis reactor 1112. In the illustrated embodiment, the pyrolysisreactor 1112 also includes an outlet 1114 configured to removesubstances such as condensable vapors and non-condensable gases androute the removed substances to the material enrichment unit 1122.

Various embodiments extend the concept of additional carbon formation byincluding a separate material enrichment unit 818, 1122 in which cooledcarbon is subjected to an environment including carbon-containingspecies, to enrich the carbon content of the final product. When thetemperature of this unit is below pyrolysis temperatures, the additionalcarbon is expected to be in the form of adsorbed carbonaceous species,rather than additional fixed carbon.

Referring now to FIG. 14 a single-reactor biomass processing unit 1400of one embodiment is illustrated. Unit 1400 comprises a hopper 1404 intowhich feedstock 1402 is fed. Hopper 1404 is optionally configured toenable addition and/or mixing of reactor off-gases (e.g., vapor stream1414) and/or additives and/or gases from external sources 1462 tofeedstock 1402 before conveying the feedstock 1402 to reactor 1412.Activated carbon 1426 is mechanically conveyed through reactor 1412before exiting at the opposite end. Steam, nitrogen, carbon dioxide, ora combination thereof 1452 is introduced into reactor 1412 in acountercurrent manner compared to the biomass path. Vapor stream 1414 isremoved at least in part from the reactor 1412 and is optionally fedinto hopper 1404, and then to a thermal oxidizer 1424. Heat exchanger1454 enables heat from the emissions of the thermal oxidizer to heat gasstream 1458, which can comprise nitrogen and/or carbon dioxide. Gasstream 1458, or a portion thereof, is recycled via path 1460 to thereactor 1412, and/or optionally to the feedstock 1402 before entry intothe reactor 1412 (not shown). Off-gases 1456 can be disposed ofaccording to standard methods, for example through a stack.

Referring now to FIG. 15 a two-reactor biomass processing unit 1500 ofone embodiment is illustrated. Unit 1500 comprises a first multizonereactor unit 1512A, configured substantially similarly to processingunit 1400 described above with respect to FIG. 14. In this embodiment,however, at least a portion of the biogenic activated carbon 1526Aproduced by reactor 1512A is fed into a hopper 1504 and then into secondreactor 1512B via path 1502. At least a portion of the optionallythermally oxidized and optionally adjusted vapor stream 1560 produced byfirst reactor 1512A, thermal oxidizer 1524 and heat exchanger 1554 isfed countercurrently into second reactor 1512B. Optionally, at least aportion of the off-gases from second reactor 1512B are recycled via path1572 to indirectly heat the second reactor 1512B. Alternatively, or inaddition, portions of the off-gases that are not recycled as heat can bedisposed of, for example by a stack, via path 1556B. Biogenic activatedcarbon product exits second reactor 1512B via path 1526B.

As will be described in detail below, there are a large number ofoptions as to intermediate input and output (purge or probe) streams ofone or more phases present in any particular reactor, various mass andenergy recycle schemes, various additives that may be introducedanywhere in the process, adjustability of process conditions includingboth reaction and separation conditions in order to tailor productdistributions, and so on. Zone or reactor-specific input and outputstreams enable good process monitoring and control, such as through FTIRsampling and dynamic process adjustments.

The present disclosure is different than fast pyrolysis, and it isdifferent than conventional slow pyrolysis. High-quality carbonmaterials in the present disclosure, including compositions with highfractions of fixed carbon, may be obtained from the disclosed processesand systems.

Exemplary Uses

Silicon products can be produced using porous carbon and some form ofsilicon dioxide in a furnace. Generally, silicon dioxide that isintroduced to silicon production furnaces needs to be relatively large(for example, tennis-ball sized). Both silica fume and raw silicon(river rock) are only capable of being used in a silicon productionfurnace when combined in a larger carbon rod which will allow theproduct to “sink” in the furnace toward the electrodes. The feedstock isbasically river rock. There is a limited supply of river rock that isboth of sufficient purity and of useful size. Disclosed herein arecompositions that overcome this problem.

Surprisingly, the inventors have found that: (1) the compositions asdescribed herein allow for the use of higher purity and/or smaller (andless expensive) sources of silicon dioxide than heretofore could be usedin silicon production furnaces, for example electric arc furnaces andsubmerged arc furnaces; (2) the proximity of the carbon and silicondioxide in the densified compositions result in more efficientconversion to silicon (therefore the closer proximity achieved throughdensification is a significant structural aspect); and (3) thecompositions, because of their greater purity (greater purity is asignificant structural aspect), improve the overall quality of any finalsilicon product produced using the compositions.

It is understood that the examples and embodiments described herein arefor illustrative purposes only and are not intended to limit the scopeof the claimed invention. It is also understood that variousmodifications or changes in light the examples and embodiments describedherein will be suggested to persons skilled in the art and are to beincluded within the spirit and purview of this application and scope ofthe appended claims. All publications, patents, and patent applicationscited herein are hereby incorporated by reference in their entirety forall purposes.

All publications, patents, and patent applications cited in thisspecification are herein incorporated by reference in their entirety asif each publication, patent, or patent application were specifically andindividually put forth herein.

Where methods and steps described above indicate certain eventsoccurring in certain order, those of ordinary skill in the art willrecognize that the ordering of certain steps can be modified and thatsuch modifications are in accordance with the variations of thedisclosure. Additionally, certain of the steps can be performedconcurrently in a parallel process when possible or performedsequentially.

Some variations of the disclosure are premised, at least in part, on thediscovery that multiple reactors or multiple zones within a singlereactor can be designed and operated in a way that optimizes carbonyield and product quality from pyrolysis, while maintaining flexibilityand adjustability for feedstock variations and product requirements.

The above description should not be construed as limiting in any way asto the potential applications of the biogenic porous carbon. Injectionof biogenic porous carbon into gas streams can be useful for control ofcontaminant emissions in gas streams or liquid streams derived fromcoal-fired power plants, biomass-fired power plants, metal processingplants, crude-oil refineries, chemical plants, polymer plants, pulp andpaper plants, cement plants, waste incinerators, food processing plants,gasification plants, and syngas plants.

EXAMPLES Example 1. Preparation of Silicon Dioxide Biogenic PorousCarbon Composition—General Method

Woody biomass (red pine sawdust) was loaded into a hopper and conveyedoptionally to a dryer where moisture in the wood was reduced below 15%and the biomass was then conveyed to a reactor system as describedherein where the biomass was heated to approximately 650 degrees Celsiusfor approximately 30 minutes and activated with a gas stream comprisedprimarily of CO₂ and H2O. Porous carbon was then discharged from thereactor and cooled with N2 and H2O and conveyed to a mixer where 25% byweight of silicon dioxide was introduced and mixed with the porouscarbon for approximately 5 minutes. The mixed silicon dioxide biogenicporous carbon composition was then conveyed to an extruder where it wasextruded into pellets of approximately 0.25 inches×1 inch, which werethen sent to dryer and dried to below approximately 8 percent moisture.

From the foregoing, it will be appreciated that specific embodiments ofthe invention have been described herein for purposes of illustration,but that various modifications may be made without deviating from thescope of the invention. Accordingly, the invention is not limited exceptas by the appended claims.

Para. A. A high-carbon biogenic reagent composition comprising, on a drybasis: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andsilicon dioxide; wherein the total carbon comprises biogenic carbon.

Para. B. A high-carbon biogenic reagent composition comprising, on a drybasis: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andsilicon dioxide; wherein the silicon dioxide is comprised within riverrock; and wherein the total carbon comprises biogenic carbon.

Para. C. A high-carbon biogenic reagent composition comprising, on a drybasis: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andsilicon dioxide; wherein the silicon dioxide is comprised within silicafume; and wherein the total carbon comprises biogenic carbon.

Para. D. The high-carbon biogenic reagent composition of Para. A,wherein the silicon dioxide is comprised within river rock.

Para. E. The high-carbon biogenic reagent composition of Para. A,wherein the silicon dioxide is comprised within silica fume.

Para. F. The high-carbon biogenic reagent composition of any one ofParas. A to E, comprising at least about 65 wt % total carbon.

Para. G. The high-carbon biogenic reagent composition of any one ofParas. A to F, comprising at least about 70 wt % total carbon.

Para. H. The high-carbon biogenic reagent composition of any one ofParas. A to G, comprising at least about 95 wt % total carbon.

Para. I. The high-carbon biogenic reagent composition of any one ofParas. A to H, comprising at least about 15 wt % silicon dioxide.

Para. J. The high-carbon biogenic reagent composition of any one ofParas. A to J, comprising at least about 25 wt % silicon dioxide.

Para. K. The high-carbon biogenic reagent composition of any one ofParas. A to J, comprising at least about 1 wt % silicon dioxide.

Para. L. The high-carbon biogenic reagent composition of any one ofParas. A to K, wherein the high-carbon biogenic reagent composition hasbeen extruded.

Para. M. The high-carbon biogenic reagent composition of any one ofParas. A to L, wherein the high-carbon biogenic reagent composition hasbeen densified.

Para. N. The high-carbon biogenic reagent composition of any one ofParas. A to M, wherein the high-carbon biogenic reagent composition ispellet shaped.

Para. O. The high-carbon biogenic reagent composition of any one ofParas. A to N, wherein the high-carbon biogenic reagent composition hasdimensions of at least about 0.64 cm (0.25 in) by about 2.5 cm (1.0 in)to at most about 5.1 cm (2.0 in) by about 15 cm (6.0 in).

Para. P. The high-carbon biogenic reagent composition of any one ofParas. A to O, wherein the high-carbon biogenic reagent composition hasa bulk density of about 560 to about 720 kg/m³ (35 to 45 lb/ft³).

Para. Q. The high-carbon biogenic reagent composition of any one ofParas. A to P, wherein the high-carbon biogenic reagent composition hasan iodine number of at least about 300.

Para. R. A high-carbon biogenic reagent composition comprising, on a drybasis: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andat least about 15 wt % silicon dioxide; wherein the silicon dioxide iscomprised within river rock; wherein the total carbon comprises biogeniccarbon; and wherein the high-carbon biogenic reagent composition hasbeen densified, is pellet shaped with dimensions of at least about 0.64cm (0.25 in) by about 2.5 cm (1.0 in), and has a bulk density of about560 to about 720 kg/m³ (35 to 45 lb/ft³).

Para. S. A high-carbon biogenic reagent composition comprising, on a drybasis: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andat least about 15 wt % silicon dioxide; wherein the silicon dioxide iscomprised within silica fume; wherein the total carbon comprisesbiogenic carbon; and wherein the high-carbon biogenic reagentcomposition has been densified, is pellet shaped with dimensions of atleast about 0.64 cm (0.25 in) by about 2.5 cm (1.0 in), and has a bulkdensity of about 560 to about 720 kg/m³ (35 to 45 lb/ft³).

Para. T. A process for producing a high-carbon biogenic reagent, saidprocess comprising: providing a carbon-containing feedstock comprisingdry biomass; in a preheating zone, preheating said feedstock in thepresence of a substantially inert gas for at least about 5 minutes andwith a preheating temperature selected from about 80° C. to about 500°C.; in a pyrolysis zone, pyrolyzing said feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases; separating at least a portion of said condensable vapors and atleast a portion of said non-condensable gases from said hot pyrolyzedsolids; in a cooling zone, cooling said hot pyrolyzed solids, in thepresence of said substantially inert gas for at least about 5 minutesand with a cooling temperature less than said pyrolysis temperature, togenerate warm pyrolyzed solids; in a cooler that is separate from saidcooling zone, cooling said warm pyrolyzed solids to generate coolpyrolyzed solids; and recovering a high-carbon biogenic reagentcomprising at least a portion of said cool pyrolyzed solids; wherein theprocess further comprises introducing silicon dioxide into said process.

Para. U. The process of Para. T, further comprising drying saidfeedstock to remove at least a portion of moisture, if any, containedwithin said feedstock prior to preheating said feedstock.

Para. V. The process of Para. T or U, further comprising deaerating saidfeedstock to remove at least a portion of molecular oxygen, if any,contained with said feedstock prior to preheating said feedstock.

Para. W. The process of any one of Paras. T to V, wherein introducingsilicon dioxide comprises introducing silica fume.

Para X. The process of any one of Paras. T to W, wherein introducingsilicon dioxide comprises introducing river rock.

Para. Y. The process of any one of Paras. T to X, further comprisingdensification.

Para. Z. The process of any one of Paras. T to Y, further comprisingpressing, binding, pelletizing, extruding, or agglomerating thehigh-carbon biogenic reagent.

1. A high-carbon biogenic reagent composition comprising, on a drybasis: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andsilicon dioxide; wherein the total carbon comprises biogenic carbon.2-3. (canceled)
 4. The high-carbon biogenic reagent composition of claim1, wherein the silicon dioxide is comprised within river rock.
 5. Thehigh-carbon biogenic reagent composition of claim 1, wherein the silicondioxide is comprised within silica fume.
 6. The high-carbon biogenicreagent composition of claim 1, comprising at least about 65 wt % totalcarbon.
 7. (canceled)
 8. The high-carbon biogenic reagent composition ofclaim 1, comprising at least about 95 wt % total carbon.
 9. Thehigh-carbon biogenic reagent composition of claim 1, comprising at leastabout 15 wt % silicon dioxide.
 10. The high-carbon biogenic reagentcomposition of claim 1, comprising at least about 25 wt % silicondioxide.
 11. The high-carbon biogenic reagent composition of claim 1,comprising at least about 1 wt % silicon dioxide.
 12. The high-carbonbiogenic reagent composition of claim 1, wherein the high-carbonbiogenic reagent composition has been extruded.
 13. The high-carbonbiogenic reagent composition of claim 1, wherein the high-carbonbiogenic reagent composition has been densified.
 14. The high-carbonbiogenic reagent composition of claim 1, wherein the high-carbonbiogenic reagent composition is pellet shaped.
 15. The high-carbonbiogenic reagent composition of claim 1, wherein the high-carbonbiogenic reagent composition has dimensions of at least about 0.64 cm(0.25 in) by about 2.5 cm (1.0 in) to at most about 5.1 cm (2.0 in) byabout 15 cm (6.0 in).
 16. The high-carbon biogenic reagent compositionof claim 1, wherein the composition has a bulk density of about 560 toabout 720 kg/m³ (35 to 45 lb/ft³).
 17. The high-carbon biogenic reagentcomposition of claim 1, wherein the high-carbon biogenic reagentcomposition has an iodine number of at least about
 300. 18. Thehigh-carbon biogenic reagent composition of claim 1, comprising: atleast about 50 wt % total carbon, at most about 5 wt % hydrogen, at mostabout 1 wt % nitrogen, at most about 0.5 wt % phosphorus, at most about0.2 wt % sulfur, at most about 0.02 wt % titanium, at most about 0.5%calcium, at most about 0.1% aluminum, and at least about 15 wt % silicondioxide; wherein the silicon dioxide is comprised within river rock;wherein the total carbon comprises biogenic carbon; and wherein thehigh-carbon biogenic reagent composition has been densified, is pelletshaped with dimensions of at least about 0.64 cm (0.25 in) by about 2.5cm (1.0 in), and has a bulk density of about 560 to about 720 kg/m³ (35to 45 lb/ft³).
 19. The high-carbon biogenic reagent composition of claim1, comprising: at least about 50 wt % total carbon, at most about 5 wt %hydrogen, at most about 1 wt % nitrogen, at most about 0.5 wt %phosphorus, at most about 0.2 wt % sulfur, at most about 0.02 wt %titanium, at most about 0.5% calcium, at most about 0.1% aluminum, andat least about 15 wt % silicon dioxide; wherein the silicon dioxide iscomprised within silica fume; wherein the total carbon comprisesbiogenic carbon; and wherein the high-carbon biogenic reagentcomposition has been densified, is pellet shaped with dimensions of atleast about 0.64 cm (0.25 in) by about 2.5 cm (1.0 in), and has a bulkdensity of about 560 to about 720 kg/m³ (35 to 45 lb/ft³).
 20. A processfor producing a high-carbon biogenic reagent, said process comprising:providing a carbon-containing feedstock comprising dry biomass; in apreheating zone, preheating said feedstock in the presence of asubstantially inert gas for at least about 5 minutes and with apreheating temperature selected from about 80° C. to about 500° C.; in apyrolysis zone, pyrolyzing said feedstock in the presence of asubstantially inert gas for at least about 10 minutes and with apyrolysis temperature selected from about 250° C. to about 700° C., togenerate hot pyrolyzed solids, condensable vapors, and non-condensablegases; separating at least a portion of said condensable vapors and atleast a portion of said non-condensable gases from said hot pyrolyzedsolids; in a cooling zone, cooling said hot pyrolyzed solids, in thepresence of said substantially inert gas for at least about 5 minutesand with a cooling temperature less than said pyrolysis temperature, togenerate warm pyrolyzed solids; in a cooler that is separate from saidcooling zone, cooling said warm pyrolyzed solids to generate coolpyrolyzed solids; and recovering a high-carbon biogenic reagentcomprising at least a portion of said cool pyrolyzed solids; wherein theprocess further comprises introducing silicon dioxide into said process.21. The process of claim 20, further comprising drying said feedstock toremove at least a portion of moisture, if any, contained within saidfeedstock prior to preheating said feedstock.
 22. (canceled)
 23. Theprocess of claim 20, wherein introducing silicon dioxide comprisesintroducing silica fume.
 24. The process of claim 20, whereinintroducing silicon dioxide comprises introducing river rock. 25-26.(canceled)